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DOE OSTI2020

Mechanical and chemical properties of PVD and cold spray Cr-coatings on Zircaloy-4

In this paper, accident-tolerant fuel (ATF) cladding materials aim to improve fuel reliability and safety during accident scenarios in water-cooled reactors. These ATF cladding should also perform comparable or better than the current zirconium alloy cladding under reactor normal operating conditions. Surface-modified Zircaloy-4 was produced by depositing a protective coating of chromium by two different coating techniques, Physical Vapor Deposition (PVD) and Cold Spray (CS). The coating thickness, structure, composition, and mechanical properties of the coated Zircaloy were assessed with advanced materials characterization techniques. Results showed a strengthening effect of the Cr-coating, along with ~83% higher hardness compared to that of the Zircaloy-4 substrate. Surface topography and surface chemistry of the Cr-coated Zircaloy-4 were assessed with contact profilometry, atomic force microscopy, contact angle goniometry, and X-ray photoelectron spectroscopy. Deposited Cr-coating significantly improved surface wettability compared to the substrate Zircaloy-4. The formation of surface oxides on the coatings by prolonged exposure to ambient air showed a further increase in the hydrophobic behavior. Surface parameters and surface chemistry after flow boiling critical heat flux tests, conducted at atmospheric pressure, evidenced a slight increase in surface roughness with notable changes in wettability associated with the formation of surface oxides.

36 MATERIALS SCIENCE↗

NASA NTRS2003

Gamma-Ray Bursts and Cosmology

The unrivalled, extreme luminosities of gamma-ray bursts (GRBs) make them the favored beacons for sampling the high redshift Universe. To employ GRBs to study the cosmic terrain -- e.g., star and galaxy formation history -- GRB luminosities must be calibrated, and the luminosity function versus redshift must be measured or inferred. Several nascent relationships between gamma-ray temporal or spectral indicators and luminosity or total energy have been reported. These measures promise to further our understanding of GRBs once the connections between the luminosity indicators and GRB jets and emission mechanisms are better elucidated. The current distribution of 33 redshifts determined from host galaxies and afterglows peaks near z $\sim$ 1, whereas for the full BATSE sample of long bursts, the lag-luminosity relation predicts a broad peak z $\sim$ 1--4 with a tail to z $\sim$ 20, in rough agreement with theoretical models based on star formation considerations. For some GRB subclasses and apparently related phenomena -- short bursts, long-lag bursts, and X-ray flashes -- the present information on their redshift distributions is sparse or entirely lacking, and progress is expected in Swift era when prompt alerts become numerous.

Norris, Jay P.↗

NASA NTRS2005

Relative Ages of the Highlands, Lowlands, and Transition Zone Along a Portion of the Mars Crustal Dichotomy from Densities of Visible and Buried Impact Craters

Understanding the fundamental age relationships of the different parts of the Mars Crustal Dichotomy is essential to fully understanding the events that shaped the early history and formation of the surface of Mars. A dominant question is what are the true relative ages of the Northern Lowlands and the Southern Highlands? Using MOLA data from the Mars Global Surveyor and Viking visual images, a dataset of both buried and visible crater diameters was created over a nine million sq km study area of a section of the dichotomy boundary stretching from Arabia Terra to Utopia Planitia. Cumulative frequency plots on a log-log scale were used to determine the relative ages for the Highlands, the Lowlands, and the Transition Zone, separately for the visible, the buried and the combined total (visible+ buried) populations. We find the overall Highland crater population in this area is slightly older than the Lowlands, consistent with previous global studies, but the Lowlands and Transition Zone are also very old and formed at roughly the same time. It appears that the formation of the Lowlands in this region formed contemporaneously with a large-scale resurfacing event in the Highlands, perhaps caused by the process responsible for the Lowland formation.

DeSoto, G. E.↗

DOE OSTI2026

Aperture and roughness govern iron oxide passivation in olivine fractures during carbon mineralization

Efficient carbon dioxide mineralization in silicate-rich formations depends on reaction rates within fracture networks, yet the role of fracture microstructure remains poorly constrained. We investigated how fracture aperture and surface roughness influence mineralization by reacting synthetic forsteritic olivine fractures with controlled apertures (0.5–1.6 millimeters) and roughness (6–16 micrometers) with supercritical carbon dioxide at 13.7 megapascals and 185 degrees Celsius. Optical microscopy and Raman spectroscopy showed that rougher fracture surfaces promoted iron oxide precipitation, which passivated olivine surfaces, limiting magnesium availability for carbonate formation while removing iron as a reactant. These effects were more pronounced in smaller-aperture fractures. A geochemical model incorporating surface topography and passivation reproduced the observed trends, confirming that increased roughness can reduce reactivity despite greater surface area. Our results demonstrate that fracture microstructure strongly influences iron oxide passivation and carbon dioxide mineralization, with important implications for predicting long-term performance of engineered carbon dioxide storage systems.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1993

Hellas basin, Mars: Formation by oblique impact

Hellas, a 2,000-km-diameter, roughly circular multiring impact basin in the southern highlands of Mars, has a pronounced southeastern lobe of rim material that extends for some 1,500 km. This lobe and a system of ridges concentric to the southern part of the basin (including part of the lobe) were interpreted to be formed by an oblique impact that was inclined in the direction of the lobe. Our preliminary geologic mapping of the Hellas region (lat -20 to -65 deg, long 250 to 320 deg) at 1:5,000,000 scale gives this hypothesis additional supporting evidence, including a symmetric distribution of basin ejecta and volcanic centers across the inferred trend of the impact. Furthermore, measurements of relief indicate that the downrange ejecta may be about twice as thick as they are elsewhere around the rim.

Leonard, Gregory J.↗

DOE OSTI2020

Hydration and reaction mechanisms on sodium silicate glass surfaces from molecular dynamics simulations with reactive force fields

Recent development of reactive force fields have enabled molecular dynamics simulations of interactions between silicate glasses and water at the atomistic scale. While multicomponent silicate glasses encompass a wide variety of compositions and properties, one common structural feature in these glasses is the combination of the network structure that is made up of silica tetrahedra linked through corner sharing interspersed with network modifiers like alkali and alkaline-earth ions that break up the Si–O–Si linkages by forming nonbridging oxygen. In reactions with water, ion exchange between alkali ions in the glass and proton or hydronium in the solution, as well as hydrolysis reaction of the Si–O–Si linkages and subsequent silanol formation, is observed and well documented. Furthermore, we have used a set of recently developed reactive force field to investigate the reactions between water and the surfaces of silica and sodium silicate glasses of different compositions for reactions up to 8 nanoseconds. Our results indicate sodium leaching into water and diffusion of water molecules up to 25 Å into the glass surface. We examined the structural and compositional changes inside the glass and around the diffused ions and use these to explain the rates of silanol formation at the surface. We also observed proton transport in the glass which has an indirect influence on the silanol formation rates. While the surface of the glass was rough to start with, it undergoes further modification into a hydrated gel-like structure in the glass for up to 5 Å in the higher alkali containing glasses. It was found that the leached sodium ions remain close to the interface and that fragments of silicate network from the surface is capable of dislodging from the bulk glass and enter the aqueous solution. These simulations thus provide insights into the formation and structure of an alteration layers commonly observed in multicomponent silicate glasses corroded in aqueous solutions.

36 MATERIALS SCIENCE↗

NASA NTRS1973

On local inflexional instability in boundary-layer flows.

Development of a linearized theory of the two- and three-dimensional incompressible viscous flows ensuing from locally unstable velocity profiles. Indications of the theory with respect to the instability of the two-dimensional separation bubble and the mechanisms underlying formation of the turbulence wedge behind a fixed roughness element are pointed out. In connection with the aforementioned mechanisms, a theoretically based argument is advanced that, as a result of local inflectional instability of the velocity profile in a succession of skewed planes, a corresponding succession of stationary vortices is induced, the induction process terminating at the boundaries of the turbulence wedge when the velocity profiles along the boundaries themselves become unstable. It is suggested that a rational method of predicting the occurrence of roughness-induced turbulence wedges might be possible if a theory were available for the steady laminar flow caused by the roughness at a stage just prior to transition.

Tobak, M.↗

NASA NTRSDate not supplied

Exploring the Jezero Crater Floor: Overview of Results from the Mars 2020 Perseverance Rover’s First Science Campaign

The Perseverance rover embarked on its first science campaign after landing in Jezero crater on February 18, 2021 and completing ~90 days of commissioning and Ingenuity helicopter activities. During this first campaign, Perseverance explored a large swath of Jezero’s crater floor, investigating and sampling several of the topographically lowest, and potentially oldest, rocks within the crater. Crater floor units: Perseverance explored the Máaz and Séítah formations (previously mapped as the Crater Floor Fractured Rough; Cf-fr and Crater Floor Fractured 1; Cf-f-1 units[1]). These are both widespread units in the crater that potentially correlate with units outside Jezero [2-4]. The Máaz fm. was distinguished from orbit by its mafic composition and densely cratered surface, and has various hypothesized origins, including lava flows[2] and volcaniclastic airfall [3]. The Máaz fm. is important for providing age/stratigraphic constraints on the Jezero western delta. If igneous, returned Máaz fm. samples may aid in calibrating the Mars crater chronology [2,5]and understanding Mars paleomagnetism and early igneous processes(see [6]). The Séítah fm. is olivine-bearing and has been interpreted to be related to a regional unit exposed along the inner rim of Jezero crater walls and occurs more broadly in the Nili Planum and Nili Fossae region. The olivine-bearing unit and its possible correlatives has a wide range of hypothesized origins including volcaniclastic airfall, impact melt, or aeolian and fluvial deposits [2-4,7,8]. The Séítahfm.is likely the oldest unit accessible to Perseverance and represents an important part of Jezero’s pre-delta-lacustrine history. As in the Máaz fm., the lithochemistry of the samples will help studies of early Mars igneous processes. The olivine-and carbonate-bearing components of this unit may also signify habitable conditions early in Jezero’s history, samples of which would be of high geochemical and astrobiological significance, as well as for understanding the martian carbon cycle(see [9]).

Mars 2020↗

NASA NTRSDate not supplied

Material Characterization and Modeling of Room Temperature Vulcanizing Silicone

Room Temperature Vulcanizing silicone (RTV) is a high-temperature adhesive that has successfully been used as a gap-filler between Thermal Protection System (TPS) tiles for heatshields on numerous missions. It is also used to bond instrumentation plugs such as temperature and pressure sensors into the heatshields. While RTV has been traditionally assumed to be a non-porous and non-ablating material, numerous experiments have shown that RTV pyrolyzes and becomes highly porous as it is heated. Heating RTV has also shown swelling, or intumescence, which can pose unique problems that lead to roughness induced boundary-layer transition, surface oxide formation and contamination of heat shield sensors. Therefore, it is crucial to understand and model the intumescence phenomenon of RTV. As data for RTV material properties is limited, the first step in modeling RTV is to collect material properties such as pyrolysis mass-loss, microstructure change, virgin and char porosity, etc. which was performed in our initial study. Additionally, thermomechanical properties such as Young’s modulus and Poisson ratio are required for modeling the intumescence of RTV, which were taken from literature and the coefficient of thermal expansion was collected using in-situ heating and Micro Computed Tomography (µ-CT) in previous studies. Finally, numerous other properties such as pyrolysis gas properties, virgin and char thermal conductivity and specific heat were compiled from previous experiments and literature into a material database that can be used for simulations. In Porous Material Analysis Toolbox based on OpenFOAM (PATO) [4], structural mechanics coupled with material response was used for simulating the intumescence of RTV as it is heated. However, since the permeability of the material is very low, the pyrolysis gas creates an internal pressure build-up as the material is being heated, significantly contributing to the deformation of the material. To correctly characterize this phenomenon, additional physics models were implemented into PATO's stress analysis solver, and results were compared with RTV dilatometry test data as a preliminary verification case. Future work will include experiments of RTV at the Plasmatron X facility and the in-situ heating cell with µ-CT, and improvement of simulation tools to more accurately model RTV intumescence.

TPS↗

NASA NTRSDate not supplied

Material Properties and Modeling of Room Temperature Vulcanizing Silicone

PATO↗

NASA NTRS2022

Sampling of Jezero Crater Máaz Formation By Mars 2020 Perseverance Rover

Collection of samples that could be returned to Earth from the floor of Jezero crater is a major goal of the Mars 2020 mission. Laboratory analyses of these will expand exploration of Jezero, a Noachian crater on Mars characterized by a delta–lake system with high potential for habitability. The samples will also be used to test current ideas about the early planetary evolution of Mars. The Perseverance rover has collected samples from two members of the Máaz formation, mapped in orbital images as the Crater floor fractured rough unit by [1]. Type localities of the Roubion and Rochette members have been targeted and abraded prior to sample collection. Here we summarize these sampling activities and the potential of sampling the Chal member of Máaz. A similar summary for samples collected from the Séítah formation is described in Hickman-Lewis et al. (this meeting).

Mars 2020↗

DOE OSTI2020

Toward Long-Term Accurate and Continuous Monitoring of Nitrate in Wastewater Using Poly(tetrafluoroethylene) (PTFE)–Solid-State Ion-Selective Electrodes (S-ISEs)

Long-term accurate and continuous monitoring of nitrate (NO 3 – ) concentration in wastewater and groundwater is critical for determining treatment efficiency and tracking contaminant transport. Current nitrate monitoring technologies, including colorimetric, chromatographic, biometric, and electrochemical sensors, are not feasible for continuous monitoring. In this work, we addressed this challenge by modifying NO 3 – solid-state ion-selective electrodes (S-ISEs) with poly(tetrafluoroethylene) (PTFE, (C 2 F 4 ) n ). The PTFE-loaded S-ISE membrane polymer matrix reduces water layer formation between the membrane and electrode/solid contact, while paradoxically, the even more hydrophobic PTFE-loaded S-ISE membrane prevents bacterial attachment despite the opposite approach of hydrophilic modifications in other antifouling sensor designs. Specifically, an optimal ratio of 5% PTFE in the S-ISE polymer matrix was determined by a series of characterization tests in real wastewater. Five percent of PTFE alleviated biofouling to the sensor surface by enhancing the negative charge (–4.5 to –45.8 mV) and lowering surface roughness (Ra: 0.56 ± 0.02 nm). It simultaneously mitigated water layer formation between the membrane and electrode by increasing hydrophobicity (contact angle: 104°) and membrane adhesion and thus minimized the reading (mV) drift in the baseline sensitivity (“data drifting”). Long-term accuracy and durability of 5% PTFE-loaded NO 3 – S-ISEs were well demonstrated in real wastewater over 20 days, an improvement over commercial sensor longevity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Local Lattice Deformation of Tellurene Grain Boundaries by Four-Dimensional Electron Microscopy

Two-dimensional (2D) tellurene is a promising competitor for the fabrication of ultrathin optoelectronic devices belonging to a new family of monoelemental 2D materials. Furthermore, the precise fabrication and characterization of tellurene and its lattice defects is of utmost importance to determine device reliability and predict functionality, yet it remains experimentally challenging. The rapid growth of the four-dimensional scanning transmission electron microscopy (4D-STEM) technique as well as postprocessing tools now allows for structural analysis with nanometer-scale resolution over a broad range of length scales. Here, we use 4D-STEM to reveal the three-dimensional (3D) atomic structure of the characteristic grain boundary in 2D tellurium formed through a new microwave-enabled chemical self-assembly. Strain and lattice parameter maps permit the reconstruction of the roughness of the grain boundary and suggest that its formation is promoted by a wedge of helical atomic chains along the [0001] crystallographic direction. The observation of wrinkles at the grain boundary is found to be the dominant relaxation mechanism. Insights into the formation mechanism are elucidated by mapping the lattice parameters as the first demonstration of local in-plane and out-of-plane unit cell variation in a nanometer-by-nanometer real-space array.

36 MATERIALS SCIENCE↗

NASA NTRS1977

The electric fields produced by lightning stepped leaders

The electric fields produced by stepped and dart-stepped leaders which immediately precede return strokes in lightning discharges to the ground have been recorded in Florida and Arizona. The mean interval time between normal steps is about 16 microsec, and the mean interval between dart steps is 6-8 microsec. The amplitudes of leader pulses in Florida increase just prior to the return stroke, the largest usually being about 10% of the return-stroke peak. In Arizona the leader pulse amplitudes are smaller than those in Florida, in relation to the return stroke, and are not as easy to identify. The shapes of the fields produced by normal steps are similar to dart steps, and the dart steps are very similar to regular sequences of pulses produced by many intracloud discharges. The 10-90% rise times of individual step wave forms are often less than 0.3 microsec, and the full width at half maximum of a step pulse is typically 0.4-0.5 microsec under conditions where the propagation distortion is minimal. The amplitudes and the shapes of leader step wave forms suggest that the peak step current is at least 2000-8000 A close to the ground and that the maximum rate of change of step current is 6-24 kA/microsec or larger. A rough estimate of the minimum charge lowered during the formation of a step is 0.001 to 0.004 C.

Krider, E. P.↗

NASA NTRS1984

Measurements of local convective heat transfer coefficients on ice accretion shapes

The thin-skin heat rate technique was used to determine local convective heat transfer coefficients for four representative ice accretion shapes. The shapes represented three stages of glaze ice formation and one rime ice formation; the ice models had varying degrees of surface roughness. In general, convective heat transfer was higher in regions where the model's surfaces were convex and lower in regions where the surfaces were concave. The effect of roughness was different for the glaze and rime ice shapes. On the glaze ice shapes, roughness increased the maximum Nu by 80 percent, but the other Nu values were virtually unchanged. On the rime ice shape, the Nu numbers near the stagnation point were unchanged. The maximum Nu value increased by 45 percent, and the Nu number downstream of the peak increased by approximately 150 percent.

Arimilli, R. V.↗

NASA NTRS1995

The fundamental plane correlations for globular clusters

In the parameter space whose axes include a radius (core, or half-light), a surface brightness (central, or average within the half-light radius), and the central projected velocity dispersion, globular clusters lie on a two-dimensional surface (a plane, if the logarithmic quantities are used). This is analogous to the 'fundamental plane' of elliptical galaxies. The implied bivariate correlations are the best now known for globular clusters. The derived scaling laws for the core properties imply that cluster cores are fully virialized, homologous systems, with a constant (M/L) ratio. The corresponding scaling laws on the half-light scale are differrent, but are nearly identical to those derived from the 'fundamental plane' of ellipticals. This may be due to the range of cluster concentrations, which are correlated with other parameters. A similar explanation for elliptical galaxies may be viable. These correlations provide new empirical constraints for models of globular cluster formation and evolution, and may also be usable as rough distance-indicator relations for globular clusters.

Djorgovski, S.↗

NASA NTRSDate not supplied

Efficient Parametric Uncertainty Analysis of an Earth Entry Vehicle Concept Using Least Angle Regression

The objective of this work was to outline and apply an efficient and accurate parametric un-certainty propagation approach to the analysis of convective heating on an Earth entry vehicle concept. The described approach was based on Least Angle Regression used to solve a sparse and underdetermined linear system in the point-collocation non-intrusive polynomial chaos surrogate method. This approach involved an iterative process to computing the non-zero terms of the underlying polynomial chaos model using only enough samples to converge uncertainty interval predictions and Sobol index values based global nonlinear sensitivity estimates. The Earth entry vehicle was analyzed at three points along a representative trajectory for a Mars return mission. 329 sources of uncertainty were identified in the computational fluid dynamics model used to predict the forebody convective heating. These included uncertainty in flow field chemical rates, collision integrals, heats of formation, surface finite rate char model reaction rates, wall roughness height, and the turbulent Schmidt number. Results from this study showed that convective heating uncertainty as high as 50% of the nominal was predicted with only about 50 evaluations of the computational model. This was far fewer than would be required for a sampling-based approach or a full basis polynomial chaos model, which would have required over 50,000 samples. Additionally, results showed that over 90% of the total convective heating uncertainty was due to uncertainty in the N2catalytic rate on the surface, while the remainder of the uncertainty was attributed to the turbulent Schmidt number and the wall roughness uncertainties.

Thomas K West IV↗

NASA NTRSDate not supplied

Towards Quantifying and Correlating RTV Intumescence to Entry-Relevant Conditions

Room Temperature Vulcanizing silicone (RTV) is a high-temperature adhesive used as a gap-filler between Thermal Protection System (TPS) tiles for heatshields on numerous missions. It is also adopted to bond instrumentation plugs of temperature and pressure sensors into heatshield’s tiles. While RTV has been traditionally assumed to be a non-porous and non-ablating material, numerous experiments have shown that RTV pyrolyzes and becomes highly porous as it is heated. Experimental data has also shown heating rate-dependent swelling (or intumescence) and shrinking of RTV, these volume changes may cause roughness-induced boundary layer transition. Outgassing and surface oxide formation of RTV upon decomposition also occur, which can be sources of contamination of heat shield sensors. This combination of detrimental effects motivates a critical need to develop a high-fidelity model for RTV ablation. As a first critical step in RTV modeling, a comprehensive material properties database for RTV was collected that account for the lack of data in properties such as pyrolysis char yield, shape change, virgin and char porosity. The next step is to quantify the volume change of RTV as a function of temperature. While this was done in previous campaigns, limited data was collected which showed a possible heating rate dependent intumescent behavior. To further understand the intumescence phenomenon of RTV, numerous dedicated experiments were performed at Beamline 8.3.2 of the Advanced Light Source, where RTV samples were heated while X-ray scans were taken in situ. Micro-Computed Tomography scans were taken in situ for low heating rates (≤ 60 °C/min), whereas continuous radiography scans were taken for higher heating rates (≤ 1500 ºC/min). Unconstrained samples and samples constrained in different holders (quartz, graphite, FiberForm and PICA) were tested to determine the change in intumescence due to confinement. Using deep learning techniques, the tomographies and radiographies are segmented to obtain volume change, porosity, pore size distributions and connectivity. From the results obtained, modifications to the previous RTV intumescence model are proposed, along with preliminary comparisons to testing RTV at high-enthalpy facilities.

RTV↗