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At least 127 records · Page 7

Huygens Crater: Insights into Noachian Volcanism, Stratigraphy, and Aqueous Processes

Huygens crater is a well preserved peak ring structure on Mars centered at 13.5 deg S, 55.5 deg E in the Noachian highlands between Terras Tyrrhena and Sabaea near the NW rim of Hellas basin. With a diameter of approximately 470 km, it uplifted and exhumed pre-Noachian crustal materials from depths greater than 25 km, penetrating below the thick, ubiquitous layer of Hellas ejecta. In addition, Huygens served as a basin for subsequent aqueous activity, including erosion/deposition by fluvial valley networks and subsurface alteration that is now exposed by smaller impacts. Younger mafic-bearing plains that partially cover the basin floor and surrounding intercrater areas were likely emplaced by later volcanism.

Ackiss, S. E.↗

The Effects of Contaminant-Aging on Decontamination Efficacy for Rapid Remediation of Concrete Surfaces - 20412

Understanding the relationship between decontamination efficacy and contaminant aging is imperative for developing effective remediation strategies following a large-scale contamination event. Non-destructive decontamination of concrete following a contamination incident becomes more difficult with increased time between contamination and decontamination because contaminants may chemically bind to concrete and/or penetrate into the concrete subsurface. In this work, we evaluated the decontamination efficacy of two decontamination methods on concrete samples contaminated with soluble Cesium-137 (Cs-137) and silica particles with 0.5 μm and 2 μm diameters. Concrete samples were aged between 1 and 59 days, with half of the coupons receiving 1 mL of artificial rainwater about once every three days. After aging, coupons were either decontaminated or analyzed to determine contaminant penetration depths. Coupons were decontaminated with 0.1 M Potassium Chloride (KCI) solution applied either by flowing solution across the contaminated coupon face or non-destructive power washing. Contaminant depth profiles were created by removing the top surface of the coupon at least 15 times, measuring the activity in each removed layer, normalizing the total activity removed to the measured decontamination efficacy following the last layer removal, and determining the penetration thickness using the coupon dimensions, bulk density, and mass of material removed for each layer. Pressurized washing effectively removed particles, but not soluble cesium, despite the majority of Cs-137 being located within the first millimeter of the subsurface. Soluble cesium removal by flowing 0.1 M KCI solution across the contaminated surface dropped to less than 12% within the first ten days. This drop in Cs-137 removal efficacy occurred within the first five days for coupons experiencing artificial rainfall events. Flowing 0.1 M KCI solution across the contaminated face was ineffective at removing particles, likely because particles had localized in surface depressions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Hand-Held Units for Short-Range Wireless Biotelemetry

Special-purpose hand-held radiotransceiver units have been proposed as means of short-range radio powering and interrogation of surgically implanted microelectromechanical sensors and actuators. These units are based partly on the same principles as those of the units described in "Printed Multi- Turn Loop Antennas for RF Biotelemetry" (LEW-17879-1), NASA Tech Briefs, Vol. 31, No. 6 (June 2007), page 48. Like the previously reported units, these units would make it unnecessary to have wire connections between the implanted devices and the external equipment used to activate and interrogate them. Like a unit of the previously reported type, a unit of the type now proposed would include a printed-circuit antenna on a dielectric substrate. The antenna circuitry would include integrated surface-mount inductors for impedance tuning. Circuits for processing the signals transmitted and received by the antenna would be included on the substrate. During operation, the unit would be positioned near (but not in electrical contact with) a human subject, in proximity to a microelectromechanical sensor or actuator that has been surgically implanted in the subject. It has been demonstrated that significant electromagnetic coupling with an implanted device could be established at a distance of as much as 4 in. (.10 cm). During operation in the interrogation mode, the antenna of the unit would receive a radio telemetry signal transmitted by the surgically implanted device. The antenna substrate would have dimensions of approximately 3.25 by 3.75 inches (approximately 8.3 by 9.5 cm). The substrate would have a thickness of the order of 30 mils (of the order of a somewhat less than a millimeter). The substrate would be made of low-radiofrequency- loss dielectric material that could be, for example, fused quartz, alumina, or any of a number of commercially available radio-frequency dielectric composite materials. The antenna conductors would typically be made of copper or a combination of chromium and gold. The choice of metal and the thickness of the metal layer(s) would depend on the choice of substrate material. For example, on a quartz or alumina substrate, one would typically use a layer of chromium 150 A thick and a layer of gold 2 m thick. The proposed units and the implanted devices that they would interrogate or activate would be inherently safe to use. They would operate at low radiated-power levels for short interrogation times (typically, milliseconds). Hence, there would be little local heating of tissues surrounding the implanted devices and little absorption of radio energy by such sensitive body parts as the eyes and the brain. Because the implanted devices would not depend on battery power and would be activated only during short interrogation intervals and would otherwise be in the goff h state most of the time, the useful lifetimes of the implanted devices would be greater than those of comparable battery-powered implanted devices. The compactness of the hand-held transceiver units would facilitate transport and storage and would facilitate self-diagnosis by patients able to handle the units while away from medical facilities.

Miranda, Felix A.↗

Modifications of comet materials by the sublimation process: Results from simulation experiments

An active comet like comet Halley loses by sublimation a surface layer of the order of 1 m thickness per perihelion passage. In situ measurements show that water ice is the main constituent which contributes to the gas emission although even more volatile species (CO, NH3, CH4, CO2 etc.) have been identified. Dust particles which were embedded in the ices are carried by the sublimating gases. Measurements of the chemical composition of cometary grains indicate that they are composed of silicates of approximate chondritic composition and refractory carbonaceous material. Comet simulation experiments show that significant modifications of cometary materials occur due to sublimation process in near surface layers which have to be taken into account in order to derive the original state of the material.

Gruen, E.↗

Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology

Catalyzing the oxygen evolution reaction (OER) is important for key energy-storage technologies, particularly water electrolysis and photoelectrolysis for hydrogen fuel production. Under neutral-to-alkaline conditions, first-row transition-metal oxides/(oxy)hydroxides are the fastest-known OER catalysts and have been the subject of intense study for the past decade. Critical to their high performance is the intentional or accidental addition of Fe to Ni/Co oxides that convert to layered (oxy)hydroxide structures during the OER. Unraveling the role that Fe plays in the catalysis and the molecular identity of the true “active site” has proved challenging, however, due to the dynamics of the host structure and absorbed Fe sites as well as the diversity of local structures in these disordered active phases. In this Account, we highlight our work to understand the role of Fe in Ni/Co (oxy)hydroxide OER catalysts. We first discuss how we characterize the intrinsic activity of the first-row transition-metal (oxy)hydroxide catalysts as thin films by accounting for the contributions of the catalyst-layer thickness (mass loading) and electrical conductivity as well as the underlying substrate’s chemical interactions with the catalyst and the presence of Fe species in the electrolyte. We show how Fe-doped Ni/Co (oxy)hydroxides restructure during catalysis, absorb/desorb Fe, and in some cases degrade or regenerate their activity during electrochemical testing. We highlight the relevant techniques and procedures that allowed us to better understand the role of Fe in activating other first-row transition metals for OER. We find several modes of Fe incorporation in Ni/Co (oxy)hydroxides and show how those modes correlate with activity and durability. We also discuss how this understanding informs the incorporation of earth-abundant transition-metal OER catalysts in anion-exchange-membrane water electrolyzers (AEMWE) that provide a locally basic anode environment but run on pure water and have advantages over the more-developed proton-exchange-membrane water electrolyzers (PEMWE) that use platinum-group-metal (PGM) catalysts. We outline the key issues of introducing Fe-doped Ni/Co (oxy)hydroxide catalysts at the anode of the AEMWE, such as the oxidative processes triggered by Fe species traveling through the polymer membrane, pH-gradient effects on the catalyst stability, and possibly limited catalyst utilization in the compressed stack configuration. We also suggest possible mitigation strategies for these issues. Lastly, we summarize remaining challenges including the long-term stability of Fe-doped Ni/Co (oxy)hydroxides under OER conditions and the lack of accurate models of the dynamic active surface that hinder our understanding of, and thus ability to design, these catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Smectite phase separation is driven by hydration-mediated interfacial charge

Smectite clay minerals have an outsize impact on the response of clay-rich media to common stimuli, such as hydration and ion exchange, motivating extensive effort to understand behaviors resulting from these processes such as swelling and exfoliation. Smectites are common and historic systems for investigating colloidal and interfacial phenomena, with two swelling regimes commonly identified across myriad clays: osmotic swelling at high water activity and crystalline swelling at low water activity. However, no current swelling model seamlessly spans the full ranges of water, salt and clay content encountered in natural or engineered settings. Here, we show that structures previously rationalized as either osmotic or crystalline coexist as a rich array of distinct colloidal phases that differ by water content, layer stacking thickness, and curvature. We present an analytical model for intermolecular potentials among water, salt and clay in both mono- and divalent electrolytes that predicts swelling pressures across high and low water activities. Our results indicate that all clay swelling is osmotic swelling, but that the osmotic pressure of charged mineral interfaces becomes attractive and dominates that of the electrolyte at high clay activities. Global energy minima are often not reached on experimental timescales due to many local energy minima that promote long-lived intermediate states with vast differences in clay, ion, and water mobilities, leading to hyperdiffusive layer dynamics driven by variable hydration-mediated interfacial charge.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Modern developments in shear flow control with swirl

Passive and active control of swirling turbulent jets is experimentally investigated. Initial swirl distribution is shown to dominate the free jet evolution in the passive mode. Vortex breakdown, a manifestation of high intensity swirl, was achieved at below critical swirl number (S = 0.48) by reducing the vortex core diameter. The response of a swirling turbulent jet to single frequency, plane wave acoustic excitation was shown to depend strongly on the swirl number, excitation Strouhal number, amplitude of the excitation wave, and core turbulence in a low speed cold jet. A 10 percent reduction of the mean centerline velocity at x/D = 9.0 (and a corresponding increase in the shear layer momentum thickness) was achieved by large amplitude internal plane wave acoustic excitation. Helical instability waves of negative azimuthal wave numbers exhibit larger amplification rates than the plane waves in swirling free jets, according to hydrodynamic stability theory. Consequently, an active swirling shear layer control is proposed to include the generation of helical instability waves of arbitrary helicity and the promotion of modal interaction, through multifrequency forcing.

Farokhi, Saeed↗

Modern developments in shear flow control with swirl

Passive and active control of swirling turbulent jets is experimentally investigated. Initial swirl distribution is shown to dominate the free jet evolution in the passive mode. Vortex breakdown, a manifestation of high intensity swirl, was achieved at below critical swirl number (S = 0.48) by reducing the vortex core diameter. The response of a swirling turbulent jet to single frequency, plane wave acoustic excitation was shown to depend strongly on the swirl number, excitation Strouhal number, amplitude of the excitation wave, and core turbulence in a low speed cold jet. A 10 percent reduction of the mean centerline velocity at x/D = 9.0 (and a corresponding increase in the shear layer momentum thickness) was achieved by large amplitude internal plane wave acoustic excitation. Helical instability waves of negative azimuthal wave numbers exhibit larger amplification rates than the plane waves in swirling free jets, according to hydrodynamic stability theory. Consequently, an active swirling shear layer control is proposed to include the generation of helical instability waves of arbitrary helicity and the promotion of modal interaction, through multifrequency forcing.

Farokhi, S.↗

Measured gain suppression in FBK LGADs with different active thicknesses

In recent years, the gain suppression mechanism has been studied for large localized charge deposits in Low-Gain Avalanche Detectors (LGADs). LGADs are a thin silicon detector with a highly doped gain layer that provides moderate internal signal amplification. Using the CENPA Tandem accelerator at the University of Washington, the response of LGADs with different thicknesses to MeV-range energy deposits from a proton beam were studied. Three LGAD prototypes of 50 μm, 100 μm, and 150 μm were characterized. The devices' gain was determined as a function of bias voltage, incidence beam angle, and proton energy. This study was conducted in the scope of the PIONEER experiment, an experiment proposed at the Paul Scherrer Institute to perform high-precision measurements of rare pion decays. LGADs are considered for the active target (ATAR), and energy linearity is an important property for particle ID capabilities.

Particle tracking detectors↗

Intumescent Coatings as Fire Retardants

Fire-retardant paint, when activated by the heat of fire, reacts to form a thick, low-density, polymeric coating or char layer. Water vapor and sulphur dioxide are released during the intumescent reaction.

Fish, R. H.↗

Contaminant Interferences with SIMS Analyses of Microparticle Impactor Residues on LDEF Surfaces

Elemental analyses of impactor residues on high purity surface exposed to the low earth orbit (LEO) environment for 5.8 years on Long Duration Exposure Facility (LDEF) has revealed several probable sources for microparticles at this altitude, including natural micrometeorites and manmade debris ranging from paint pigments to bits of stainless steel. A myriad of contamination interferences were identified and their effects on impactor debris identification mitigated during the course of this study. These interferences included pre-, post-, and in-flight deposited particulate surface contaminants, as well as indigenous heterogeneous material contaminants. Non-flight contaminants traced to human origins, including spittle and skin oils, contributed significant levels of alkali-rich carbonaceous interferences. A ubiquitous layer of in-flight deposited silicaceous contamination varied in thickness with location on LDEF and proximity to active electrical fields. In-flight deposited (low velocity) contaminants included urine droplets and bits of metal film from eroded thermal blankets.

Simon, C. G.↗

A lipoprotein allosterically activates the CwlD amidase during Clostridioides difficile spore formation

Spore-forming pathogens like Clostridioides difficile depend on germination to initiate infection. During gemination, spores must degrade their cortex layer, which is a thick, protective layer of modified peptidoglycan. Cortex degradation depends on the presence of the spore-specific peptidoglycan modification, muramic-∂-lactam (MAL), which is specifically recognized by cortex lytic enzymes. In C . difficile , MAL production depends on the CwlD amidase and its binding partner, the GerS lipoprotein. To gain insight into how GerS regulates CwlD activity, we solved the crystal structure of the CwlD:GerS complex. In this structure, a GerS homodimer is bound to two CwlD monomers such that the CwlD active sites are exposed. Although CwlD structurally resembles amidase_3 family members, we found that CwlD does not bind Zn 2+ stably on its own, unlike previously characterized amidase_3 enzymes. Instead, GerS binding to CwlD promotes CwlD binding to Zn 2+ , which is required for its catalytic mechanism. Thus, in determining the first structure of an amidase bound to its regulator, we reveal stabilization of Zn 2+ co-factor binding as a novel mechanism for regulating bacterial amidase activity. Our results further suggest that allosteric regulation by binding partners may be a more widespread mode for regulating bacterial amidase activity than previously thought.

59 BASIC BIOLOGICAL SCIENCES↗

Intumescent Coatings as Fire Retardants

The development of fire-retardant coatings to protect surfaces which may be exposed to fire or extreme heat is a subject of intense interest to many industries. A fire-retardant paint has been developed which represents a new chemical approach for preparing intumescent coatings, and potentially, is very important to fire-prevention authorities. The requirements for a superior coating include ease of application, suitability to a wide variety of surfaces and finishes, and stability over an extended period of time within a broad range of ambient temperature and humidity conditions. These innovative coatings, when activated by the heat of a fire, react to form a thick, low-density, polymeric coating or char layer. Water vapor and sulphur dioxide are released during the intumescent reaction. Two fire-protection mechanisms thus become available: (1) the char layer retards the flow of heat, due to the extremely low thermal conductivity; and (2) water vapor and sulfur dioxide are released, providing fire quenching properties. Still another mechanism functions in cases where the char, by virtue of its high oxidation resistance and low thermal conductivity, reaches a sufficiently high temperature to re-radiate much of the incident heat load. The coatings consist of dispersions of selective salts of a nitro-amino-arornatic compound. Specifically, para-nitroaniline bisulfate and the ammonium salt of para-nitroaniline-ortho sulphuric acid (2-amino-5-nitrobenzenesulphuric acid) are used. Suitable vehicles are cellulose nitrate of lacquer grade, a nitrite-phenolic modified rubber, or epoxy-polysulfide copolymer. Three separate formulations have been developed. A solvent is usually employed, such as methylethyl ketone, butyl acetate, or toluene, which renders the coatings suitably thin and which evaporates after the coatings are applied. Generally, the intumescent material is treated as insoluble in the vehicle, and is ground and dispersed in the vehicle and solvent like an ordinary coating pigment. The char found on intumescence is better in terms of yield and physical properties than chars obtained from many previously known intumescent materials. Prior to intumescence, the coating has a density of 85 pounds per cubic foot. After intumescence, the density is approximately 0.3 pounds per cubic loot. The linear expansion of the coatings ranges from 70 to 200 times the applied coating thickness.

Parker, J. A.↗

The Role of Endolithic Cyanobacteria in the Formation of Lithified Laminae in Bahamian Stromatolites

The microboring activity of endolithic cyanobacteria plays a major role in the formation of lithified laminae in modern marine stromatolites in the Exuma Cays, Bahamas. These stromatolites are composed primarily of fine grained carbonate sand that is trapped and bound by the filamentous cyanobacteria Schizothrix sp. Periodic introduction of coccoid endolithic cyanobacteria, Solentia sp., results in formation of lithified horizons, 200 to 1000 micron thick. We used SEM and petrographic analyses to examine both naturally occurring lithified layers dominated by endoliths and fused oolitic crusts generated in the laboratory by activity of endolithic cyanobacteria (Solentia sp.). Fused grain crusts consist of micritized grains that are welded together at point contacts. Micritization results from extensive microboring and rapid (days to weeks) carbonate precipitation within the bore holes. This precipitation appears to occur concurrently with further endolithic activity within the grain, Infilling of bore holes that cross from one grain to another at point contacts results in grain welding, Thus, while microboring destroys original grain textures, at the same time the endolith activity plays a constructional role in stromatolite growth by forming lithified layers of welded grains. These framework structures help to stabilize and preserve the stromatolite deposits.

Prufert-Bebout, L.↗

Stability of Mn-Doped TiO 2 Thin-Film Anodes during Water Oxidation Reactions

Incorporating manganese atoms into TiO 2 has been shown to improve its activity for water oxidation. However, its activity has been observed to steadily degrade under constant applied potential, especially at more oxidizing applied potentials. Here, the compositional profile and electrochemical stability of Mn-doped TiO 2 (Mn:TiO 2 ) thin-film electrodes precisely fabricated by atomic layer deposition (ALD) were evaluated to elucidate the mechanisms of electrode degradation. Although ALD enables the deposition of Mn dopants throughout the film thickness, only Mn within 1.5 nm of the surface was observed to be redox active. Annealing Mn:TiO 2 films in air leads to the diffusion of Mn toward the electrode surface and oxidation of the Mn and alters the redox behavior. Annealing endows greater stability to Mn redox behavior but does not fully stabilize the water oxidation current, suggesting that the two electrochemical processes are not precisely correlated. In situ inductively coupled plasma mass spectrometry reveals that Mn is lost from Mn:TiO 2 films at potentials greater than 1.8 V vs RHE. However, the initial Mn loss is equivalent to less than a single ALD layer of MnO x . Longer-term constant potential experiments suggest that Mn is lost from up to 1 nm of the electrode surface but that this loss may account for only a portion of the diminished water oxidation activity.

atomic layer deposition↗

Enhancing CO Oxidation Activity via Tuning a Charge Transfer Between Gold Nanoparticles and Supports

Charge transfer from the supports to nanoparticles at the interface is one of the key factors to determine the catalytic performances of supported nanoparticles. In this work, we revealed that the charge transfer from semiconductor support to Au nanoparticle catalysts enhanced their activity toward CO oxidation. In this work, a novel Au/SiO 2 /Si composite system with precisely controllable SiO 2 layer thickness was fabricated to tune the magnitude of interfacial charge transfer. With the support of X-ray photoelectron spectroscopy and numerical simulations, it was demonstrated that the Schottoky barrier formed across the Au/SiO 2 /Si heterojunction led to negative charge accumulation at the surface of Au nanoparticles, which may be transferred to the antibonding orbitral of adsorbed O 2 molecules to the O-O bonds. This discovery highlights a new perspective in explaining the role of strong metal-support interactions for catalytic reactions and provides a fresh path for designing the next generation of nanocatalysts.

36 MATERIALS SCIENCE↗

Dynamic realization of emergent high-dimensional optical vortices

The dimensionality of vortical structures has recently been extended beyond two dimensions, providing additional topological complexity and robustness for high-capacity information processing and turbulence control. The generation of high-dimensional vortical structures has mostly been demonstrated in classical systems through the complex interference of fluidic, acoustic, or electromagnetic waves. However, natural materials rarely support three- or higher-dimensional vortical structures and their physical interactions. Here, we experimentally demonstrate a high-dimensional gradient thickness optical cavity (GTOC) in which the optical coupling of planar metal-dielectric multilayers implements topological interactions across multiple dimensions. At non-trivial topological phases, high-dimensional GTOC induces high-dimensional vortical structures in generalized parameter space in three, four dimensions, and beyond. These emergent high-dimensional vortical structures are observed under electro-optic tomography as optical vortex dynamics in two-dimensional real-space, employing the optical thicknesses of dielectric layers as synthetic dimensions. Our findings hold significant promise for emulating high-dimensional physics and developing active topological photonic devices.

36 MATERIALS SCIENCE↗