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At least 343 records · Page 19

Peroxide-modified titanium dioxide: a chemical analog of putative Martian soil oxidants

Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

Review↗

Impacts of the Additive Manufacturing Process on the Roughness of Engine Scale Vanes and Cooling Channels

Abstract By leveraging the additive manufacturing (AM) platform, development time and costs for turbine component testing can be reduced relative to traditional investment casting. Surface roughness is a key characteristic of the additive manufacturing process that can impact flow, heat transfer, and mechanical integrity of printed components. There are multiple design and build considerations that result in variability in surface roughness, especially when additively fabricating complicated three-dimensional vanes and internal cooling passages. This study characterizes the surface roughness of internal cooling passages, vanes, and flat external surface samples made using additive manufacturing, specifically the direct metal laser sintering process. The samples were manufactured with various wall thicknesses, layer thicknesses, build locations, build directions, and on different AM machines. A combination of computed tomography scanning and optical profilometry was used to evaluate surface roughness levels. The data indicate that the dominant factors in roughness for a given layer thickness are a function of wall thickness, build location, and build direction.

Engineering↗

The CAESAR New Frontiers Mission: 1. Expected Nature of the Returned Comet Sample

Comets are time capsules from the birth of our Solar System that record pre-solar history, the initial stages of planet formation, and the sources of prebiotic organics and volatiles for the origin of life. These capsules can only be opened in laboratories on Earth. CAESAR (Comet Astrobiology Exploration Sample Return)’s sample analysis objectives are to understand the nature of Solar System starting materials and how these components came together to form planets and give rise to life. Examination of these comet nucleus surface samples in laboratories around the world will also provide ground truth to remote observations of the innumerable icy bodies of the Solar System.

Lauretta, D. S.↗

Bayesian Learning of Adatom Interactions from Atomically Resolved Imaging Data

Atomic structures and adatom geometries of surfaces encode information about the thermodynamics and kinetics of the processes that lead to their formation, and which can be captured by a generative physical model. In this work, we develop a workflow based on a machine-learning-based analysis of scanning tunneling microscopy images to reconstruct the atomic and adatom positions, and a Bayesian optimization procedure to minimize statistical distance between the chosen physical models and experimental observations. We optimize the parameters of a 2- and 3-parameter Ising model describing surface ordering and use the derived generative model to make predictions across the parameter space. For concentration dependence, we compare the predicted morphologies at different adatom concentrations with the dissimilar regions on the sample surfaces that serendipitously had different adatom concentrations. The proposed workflow can be used to reconstruct the thermodynamic models and associated uncertainties from the experimental observations of materials microstructures. The code used in the manuscript is available at https://github.com/saimani5/Adatom_interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rotary Percussive Sample Acquisition Tool

As part of a potential Mars Sample Return campaign NASA is studying a sample caching mission to Mars, with a possible 2018 launch opportunity. As such, a Sample Acquisition Tool (SAT) has been developed in support of the Integrated Mars Sample Acquisition and Handling (IMSAH) architecture as it relates to the proposed Mars Sample Return (MSR) campaign. The tool allows for core generation and capture directly into a sample tube. In doing so, the sample tube becomes the fundamental handling element within the IMSAH sample chain reducing the risk associated with sample contamination as well as the need to handle a sample of unknown geometry. The tool's functionality was verified utilizing a proposed rock test suite that encompasses a series of rock types that have been utilized in the past to qualify Martian surface sampling hardware. The corresponding results have shown the tool can effectively generate, fracture, and capture rock cores while maintaining torque margins of no less than 50% with an average power consumption of no greater than 90W and a tool mass of less than 6kg.

Sample Acquisition and Caching (SAC)↗

Evaluation of water samples collected during LANDSAT-1 overpasses of the lower Chesapeake Bay area

Water samples were collected on 18 days when the LANDSAT-1 satellite was passing over the lower Chesapeake Bay area. A correlation between the various water parameters has been performed for the more than 300 surface samples. Six days were sufficiently cloudless that MSS digital tapes were useful for analysis. Correlation of radiance values with the water parameters revealed a low correlation for chlorophyll and good correlations with particles and sediment. The relation of total particles to sediment was linear, but varied from day to day.

Bowker, D. E.↗

MBE growth technology for high quality strained III-V layers

The III-V films are grown on large automatically perfect terraces of III-V substrates which have a different lattice constant, with temperature and Group III and V arrival rates chosen to give a Group III element stable surface. The growth is pulsed to inhibit Group III metal accumulation of low temperature, and to permit the film to relax to equilibrium. The method of the invention: (1) minimizes starting step density on sample surface; (2) deposits InAs and GaAs using an interrupted growth mode (0.25 to 2 monolayers at a time); (3) maintains the instantaneous surface stoichiometry during growth (As-stable for GaAs, In-stable for InAs); and (4) uses time-resolved RHEED to achieve aspects (1) through (3).

Grunthaner, Frank J.↗

MBE growth technology for high quality strained III-V layers

III-V films are grown on large automatically perfect terraces of III-V substrates which have a different lattice constant, with temperature and Group II and V arrival rates chosen to give a Group III element stable surface. The growth is pulsed to inhibit Group III metal accumulation to low temperature, and to permit the film to relax to equilibrium. The method of the invention 1) minimizes starting step density on sample surface; 2) deposits InAs and GaAs using an interrupted growth mode (0.25 to 2 mono-layers at a time); 3) maintains the instantaneous surface stoichiometry during growth (As-stable for GaAs, In-stable for InAs); and 4) uses time-resolved RHEED to achieve aspects (1)-14 (3).

Grunthaner, Frank J.↗

Dielectric comparison of lunar and terrestrial fines at lunar conditions

The dielectric properties of lunar fines 74241,2 in the audio-frequency range under lunarlike conditions are presented. Results suggest that volatiles are released during storage and transport of the lunar sample. Apparently, subsequent adsorption of volatiles on the sample surface alters its dielectric response. The assumed volatile influence disappears after evacuation. A comparison of the dielectric properties of lunar and terrestrial materials as a function of density, temperature, and frequency indicates that if the terrestrial sample analyzed were completely devoid of atmospheric moisture, it would present dielectric losses smaller than those of the lunar sample. It is concluded that density prevails over temperature as the controlling factor of dielectric permittivity in the lunar regolith and that dielectric losses vary slowly with depth.

Alvarez, R.↗

Aeolian removal of dust from photovoltaic surfaces on Mars

It is well documented that Mars is totally engulfed in huge dust storms nearly each Martian year. Dust elevated in these global dust storms, or in any of the numerous local dust storms could settle on photovoltaic surfaces and seriously hamper photovoltaic power system performance. Using a recently developed technique to uniformly dust simulated photovoltaic surfaces, samples were subjected to Martian-like winds in an attempt to determine whether natural aeolian processes on Mars would sweep off the settled dust. The effects of wind velocity, angle of attack, height off the Martian surface, and surface coating material were investigated. Principles which can help to guide the design of photovoltaic arrays bound for the Martian surface were uncovered. Most importantly, arrays mounted with an angle of attack approaching 45 deg show the most efficient clearing. Although the angular dependence is not sharp, horizontally mounted arrays required significantly higher wind velocities to clear off the dust. From the perspective of dust-clearing it appears that the arrays may be erected quite near the ground, but previous studies have suggested that saltation effects can be expected to cause such arrays to be covered by sand if they are set up less than about a meter from the ground. Providing that the surface chemistry of Martian dusts is comparable to our test dust, the materials used for protective coating may be optimized for other considerations such as transparency, and chemical or abrasion resistance. The static threshold velocity is low enough that there are regions on Mars which experience winds strong enough to clear off a photovoltaic array if it is properly oriented. Turbulence fences proved to be an ineffective strategy to keep dust cleared from the photovoltaic surfaces.

Gaier, James R.↗

Remote Recession Sensing of Ablative Heat Shield Materials

Material recession and charring are two major processes determining the performance of ablative heat shield materials. Even in ground testing, the characterization of these two mechanisms relies on measurements of material thickness before and after testing, thus providing only information integrated over the test time. For recession measurements, optical methods such as imaging the sample surface during testing are under investigation but require high alignment and instrument effort, therefore being not established as a standard measurement method. For char depth measurements, the most common method so far consists in investigation of sectioned samples after testing or in the case of Stardust where core extractions were performed to determine char information. In flight, no reliable recession measurements are available, except total recession after recovering the heat shield on ground. Developments of mechanical recession sensors have been started but require substantial on board instrumentation adding mass and complexity. In this work, preliminary experiments to evaluate the feasibility of remote sensing of material recession and possibly char depth through optically observing the emission signatures of seeding materials in the post shock plasma is investigated. It is shown that this method can provide time resolved recession measurements without the necessity of accurate alignment procedures of the optical set-up and without any instrumentation on board of a spacecraft. Furthermore, recession data can be obtained without recovering flight hardware which would be a huge benefit for inexpensive heat shield material testing on board of small re-entry probes, e.g. on new micro-satellite re-entry probes as a possible future application of Cubesats or RBR

instrumentation↗

Strain-Mediated Sn Incorporation and Segregation in Compositionally Graded Ge 1– x Sn x Epilayers Grown by MBE at Different Temperatures

We investigated the process of Sn incorporation and surface segregation for compositionally graded Ge 1–x Sn x epilayers grown on high-quality Ge (001) substrates. Here, the growth resulted in pseudomorphic GeSn layers with a ~6% maximal Sn fraction at a constant substrate temperature. The maximal fraction of Sn was increased to 9.0% when the growth temperature was continuously lowered while increasing the Sn flux. The analysis of surface droplets and SIMS profiles of elemental composition give evidence of Sn rejection during the growth, potentially associated with a critical energy of elastic strain. The intentional reduction of the coherent strain by decreasing the Sn flux near the sample surface has been shown to trap a higher fraction of Sn in the Ge 1–x Sn x layer and lower surface segregation. Our results demonstrate that strain relief by misfit dislocations in the compositionally graded layer is inhibited, which leads to Sn segregation. Specifically, the compressive strain in the graded Ge 1–x Sn x epilayer is effectively “zero” near the interface with the Ge substrate and increases up to about –1.5 × 10 –2 near the surface. Thus, although the nucleation of a dislocation may reduce the compressive strain for the top region of the epilayer, it is not beneficial for the bottom region.

42 ENGINEERING↗

Airborne flux measurements of ammonia over the southern Great Plains using chemical ionization mass spectrometry

Abstract. Ammonia (NH3) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere–surface exchange of nitrogen. The accurate determination of NH3 emission rates remains a challenge, partly due to the propensity of NH3 to interact with instrument surfaces, leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH3, using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample–surface interactions and achieved a 1σ precision of 10–20 pptv and an immediate 1/e response rate of < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method's capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols, and Land-Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to tens of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH3 h−1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH3 emissions from the surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ∼ 300 m above ground. We derived NH3 fluxes between 1 and 11 mol km−2 h−1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and it explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH3 area emissions inventory provided by the U.S. Environmental Protection Agency indicated overall agreement but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in situ measurements of ambient NH3 mixing ratios, and even allow for the airborne mapping of the air–surface exchange of NH3.

58 GEOSCIENCES↗

Surface analysis insight note: Synthetic line shapes, integration regions and relative sensitivity factors

Here, methods for estimating photoemission intensity from X-ray photoelectron spectroscopy data are examined. The role played by “synthetic” bell-shaped curves, integration intervals, background curves, and the use of relative sensitivity factors (RSFs) in reporting percentage atomic concentration for a sample is presented. In particular, photoemission lines with differing energy distributions obtained from the NaCl sample surface are used to demonstrate how a comparison of photoemission intensities is dependent on the line shapes, background curves, and appropriate use of RSFs.

42 ENGINEERING↗

Atmospheric Electron-induced X-Ray Spectrometer (AEXS) Instrument Development

Introduction: This paper describes the progress in data acquisition and establishing the observational capability of the AEXS instrument. The AEXS is a miniature instrument[1-4] based on the excitation of characteristic X-Ray Fluorescence (XRF) and luminescence spectra using a focused electron beam which enables nondestructive evaluation of sample surfaces in planetary ambient atmospheres. In situ operation is obtained through the use of a thin electron transmissive membrane to isolate the vacuum of the AEXS source from the outside ambient atmosphere. Thus eliminating the need for a vacuum pumped sample chamber as is common in all laboratory SEM s. The transmitted electrons impinge on the sample exciting XRF spectra from the irradiated spot on in-situ or collected samples with sub-mm to cm-scale spatial resolution at Mars atmospheric pressure. The AEXS system (Fig 1) consists of a high-energy (>10keV) electron gun encapsulated by the isolation membrane, an XRF detection and analyzer system, and a high voltage power supply. The XRF data are analyzed to determine the elemental abundance for the irradiated spots. The approach to demonstrating a proof of concept of the AEXS has been through 1) demonstrating the viability of microfabricated membranes, 2) assembling AEXS setups with increasingly integrated functional components, and 3) simulating the AEXS observational capabilities. The development of the instrument is described in detail in the poster paper[4] at this conference. This paper focuses on describing the progress of the AEXS instrument to acquire XRF data and using commercially available software to analyze the data streams and determine the accuracy, precision and resolution of the analysis compared to the certified elemental abundance.

Urgiles, E.↗

The Search for Lunar Mantle Rocks Exposed on the Surface of the Moon

The lunar surface is ancient and well-preserved, recording Solar System history and planetary evolution processes. Ancient basin-scale impacts excavated lunar mantle rocks, which are still expected to be present on the surface. Sampling these rocks would provide insight into fundamental planetary processes, including differentiation and magmatic evolution. There is contention among lunar scientists as to what lithologies make up the upper lunar mantle, and where they may have been exposed on the surface. We review dynamical models of lunar differentiation in the context of recent experiments and spacecraft data, assessing candidate lithologies, their distribution, and implications for lunar evolution.

Geochemistry↗

ARPA-E PNDIODES "PN Junctions by Ion Implantation" Project (Final Report)

Electricity accounts for nearly 40% of the energy generated in the United States, of which 65% is lost to electrical system inefficiency before reaching end-use sectors. Power electronics will play a growing role in this distribution and end-use, with up to 80% of electricity estimated to pass through power electronics from generation to consumption by 2030. This gives technical improvements in power electronics enormous potential to drive efficiency gains throughout the U.S. economy. Current Si-based power architectures including MOSFETs and IGBTs are limited by high losses, low switching frequency, and poor high-temperature performance. Given the material properties of GaN, devices can exhibit a given turn-on resistance and breakdown voltage with a minute fraction of the area of a Si device—all with higher switching speeds. While n-type doping of III-nitrides has reached a high level of maturity and integration into commercialized products, p-type doping presents distinct challenges that requires continued research. The success of the next generation of GaN-based power devices depends in large part on the ability to form selective-area p-type regions, which can be accomplished by ion implantation of the prevailing acceptor dopant, Mg. This approach is relatively inexpensive and is a fab-ready processing step for creation of current-generation power electronic devices including BJTs, IGBTs, and diode rectifiers. However, ion implantation induces lattice damage and creates point defects within the material, which negatively impacts dopant activation annealing. These forms of damage may be removed by high-temperature annealing, however short annealing time and higher pressures are required to prevent decomposition of the material. We approach this challenge through an innovative combination of approaches toward obtaining high-conductivity p-type GaN. By the novel employment of a gyrotron, a microwave source that can be shaped into a highly localized beam to dissipate very high power in a semiconductor target, a wafer of GaN can be annealed in short (<2 s) ‘pulses’ at temperatures of 1450 °C (2640 °F) to achieve p-type activation without appreciable surface degradation. The p-type activation of Mg-implanted GaN can be further aided by co-implantation with N, believed to enhance the removal of point defects that compensate the acceptors dopant. Elevation to such high temperatures for even a short time induces degradation of GaN-to overcome, we have implemented additional measures to retain high-quality crystalline GaN while removing implant damage and activating Mg dopant. A bilayer cap of AlN is deposited by a combination of chemical and physical vapor deposition to protect the GaN surface. To prevent decomposition of GaN loss of N during annealing, a custom vessel—to contain pressurized N while allowing injection of microwave energy—is employed. By detailed study of the interaction of various measures that are implemented to protect the sample surface (GaN), activate the implanted dopants, and mitigate damage of the lattice heating damage during annealing, we are able to achieve p-type GaN and observe recovery of the crystal and removal of substantial density of defects created during the implantation process.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry

Ammonia (NH 3 ) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere-surface exchange of nitrogen. It is recognized as a major source of aerosol pollution, and it may limit the formation of cloud nuclei in remote or cold parts of the atmosphere. For soil and plants, NH 3 -mediated nitrogen can act as a harmful pollutant or as a desirable nutrient, mostly in natural and agricultural settings, respectively. Agriculture is also the main source of atmospheric NH 3 via volatilization from fertilizers and manure processing in livestock farming. The accurate determination of NH 3 emission rates remains a challenge, partly due to the propensity of NH 3 to interact with instrument surfaces leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH 3 , using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample-surface interactions and achieved a 1-σ precision of 10–20 pptv and an immediate 1/e response rate < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method’s capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to 10s of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH 3 h –1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH 3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH 3 emissions from surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ~300 m above ground. We derived NH 3 fluxes between –4 and 18 mol km –2 h –1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH 3 area emissions inventory provided by the US Environmental Protection Agency indicated overall agreement, but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in-situ measurements of ambient NH 3 mixing ratios, and even allow for the airborne mapping of the air-surface exchange of NH 3 .

54 ENVIRONMENTAL SCIENCES↗