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At least 73 records · Page 4

A study of the properties of beryllium doped silicon with particular emphasis on diffusion mechanisms: Profiles of depth dependent conductivity as determined by electrical surface probes

Very large diffusion coefficients were encountered and required the determination of impurity profiles for samples approximately 1 cm thick. Since conductivity values are readily converted into concentrations of electrically active impurities, the major problem became that of accurately determining the conductivity profiles of beryllium diffused silicon samples. Four-point probe measurements on samples having depth conductivities are interpreted in terms of conductivity profiles, based on an exact solution of the problem of exponentially depth dependent conductivity. Applications include surface conductivity determination where the form of the conductivity profile is known, and conductivity profile determination from probe measurements taken as the sample surface is progressively lapped away. The application is limited to samples having conductivity monotonically decreasing with depth from the probed surface.

Franks, R. K.↗

Optimizing aluminum oxide passivation layers—Laser-induced plasmas for layer formation, real-time diagnostics, and layer evaluation

Molten salts have beneficial thermophysical and electrolytic properties, but the aggressive nature of molten salts requires corrosion mitigation strategies, such as structural material surface treatment. In this study, a laser-induced breakdown spectroscopy (LIBS) system was used to simultaneously ablate and monitor de-excitation spectra to form and identify dense alumina passivation layers. Additionally, high-frequency (kHz) LIBS imaging allowed rapid elemental mapping and depth profiling for surface O/Al ratios via minimally destructive analysis. The paired t-test rejected the null hypothesis that air and Ar cover gases were equivalent (p = 0.00012), and the analysis of variance (ANOVA) showed that overlap between shots (p = 0.03112) and cover gas flow rate (p = 0.02729) were statistically significant. At 75% overlap, the O/Al ratio increased to 10% ± 2%, and 90% overlap rose further to 31% ± 2%. Regardless of overlap, tuning the gas flow from 0.5 to 2.5 L min −1 enhanced the O/Al ratio by 24% ± 4%. LIBS depth profiling showed a 3× increase in layer thickness from 75% to 90% overlap. Molecular band peaks of AlO, a precursor to Al 2 O 3 found during treatment, suggest that band intensity could be used for real-time Al 2 O 3 optimization. Ultimately, by adjusting laser spot overlap and cover gas flow rate, a 266 nm laser was shown to form Al 2 O 3 layers on an Al6061 sample, with cover gas flow rate primarily affecting the O/Al ratio and layer thickness correlating with laser spot overlap. This combination of molecular spectra collection, imaging, and depth profiling demonstrated the robust layer analysis capabilities of LIBS.

Corrosion↗

Cosmic ray production curves below reworking zones

A method is presented for calculating cosmic ray production profiles below reworking zones. The method uses an input reworking depth determined from data such as signatures in the depth profile of ferromagnetic resonance intensity and input cosmic ray production profiles for an undisturbed surface. Reworking histories are simulated using Monte Carlo techniques, and depth profiles are used to determine cosmic ray exposure age limits with a specified probability. It is shown that the track density profiles predict cosmic ray exposure ages in lunar cores that are consistent with values determined by other methods. Results applied to neutron fluence and spallation rare gases eliminate the use of reworking depth as an adjustable parameter and give cosmic ray exposure ages that are compatible with each other.

Blanford, G. E.↗

Design of the Experimental Exposure Conditions to Simulate Ionizing Radiation Effects on Candidate Replacement Materials for the Hubble Space Telescope

In this effort, experimental exposure times for monoenergetic electrons and protons were determined to simulate the space radiation environment effects on Teflon components of the Hubble Space Telescope. Although the energy range of the available laboratory particle accelerators was limited, optimal exposure times for 50 keV, 220 keV, 350 keV, and 500 KeV electrons were calculated that produced a dose-versus-depth profile that approximated the full spectrum profile, and were realizable with existing equipment. For the case of proton exposure, the limited energy range of the laboratory accelerator restricted simulation of the dose to a depth of .5 mil. Also, while optimal exposure times were found for 200 keV, 500 keV and 700 keV protons that simulated the full spectrum dose-versus-depth profile to this depth, they were of such short duration that the existing laboratory could not be controlled to within the required accuracy. In addition to the obvious experimental issues, other areas exist in which the analytical work could be advanced. Improved computer codes for the dose prediction- along with improved methodology for data input and output- would accelerate and make more accurate the calculational aspects. This is particularly true in the case of proton fluxes where a paucity of available predictive software appears to exist. The dated nature of many of the existing Monte Carlo particle/radiation transport codes raises the issue as to whether existing codes are sufficient for this type of analysis. Other areas that would result in greater fidelity of laboratory exposure effects to the space environment is the use of a larger number of monoenergetic particle fluxes and improved optimization algorithms to determine the weighting values.

Smith, L. Montgomery↗

Viscosity estimates for the crust and upper mantle from patterns of lacustrine shoreline deformation in the Eastern Great Basin

The deformed shorelines of Lake Bonneville constitute a classic source of information on lithospheric elastic thickness and upper mantle viscosity. We describe and apply a new model to a recently augmented data set. New data better constrain both the complex spatio-temporal pattern of the lake load and the crustal deformation response to that load. The history of lake level fluctuations has been significantly refined and somewhat modified. This is due to both more radiocarbon dates from within the Bonneville basin and to an improved calibration of the radiocarbon timescale itself. The data which constrain the crustal deformation pattern consist of ages and shoreline elevations from several hundred points which sample three major levels of Lake Bonneville and corresponding elevations from the high stands of three smaller lakes situated to the west of Lake Bonneville. The geometry of the Earth model incorporates an arbitrary number of layers overlying a half-space, and the rheology of each level can accommodate an arbitrary number of Maxwell viscoelastic elements in parallel. The inverse modeling comprises three complementary approaches: for the simplest configurations, we performed a direct search of the parameter space and delineated the irregular boundary of the subspace of acceptable models. For more complex configurations, we constrained the elastic parameters to their seismically determined values and then solved for viscosity versus depth profiles by either expressing the log(viscosity) versus log(depth) profile as a series of specially constructed orhtogonal polynomials, or by allowing each of 8-10 layers (plus the half-space) to have an independently determined viscosity. We found that the data do not strongly support (nor can they conclusively exclude) a more complex rheology than simple Maxwell viscoelasticity. The orthogonal polynomial solution exhibits an essentially monotonic decrease in viscosity with depth.

Bills, Bruce G.↗

Oxidation of commercial purity titanium

The oxidation kinetics of commercial purity Ti-A55 exposed to laboratory air in the 593-760 C temperature range were continuously monitored by thermogravimetric analysis. The oxide thickness was measured by microscopy, and the substrate contamination was estimated from microhardness measurements. The microhardness depth profiles were converted to oxygen composition profiles using calibration depth. The oxygen diffusion coefficient in alpha-Ti appears to be approximately concentration-independent in the 1-10 at. pct oxygen range. Diffusion coefficient for oxygen in TiO2 has been estimated as a function of temperature and is found to be about 50 times the value in alpha-Ti. The metallographically prepared cross sections of the oxidized specimens revealed a 'moving boundary' in the substrate, parallel to the oxide-metal interface. This boundary was associated with a specific oxygen level of 5.0 + or - 0.5 at. pct. It occurred at a distance from the oxide-metal interface which was correlatable with temperature and time of exposure. The diffusion coefficient corresponding to the composition of this moving boundary is in excellent agreement with the effective diffusion coefficient for the substrate contamination.

Unnam, J.↗

Design and fabrication of a reflection far ultraviolet polarizer and retarder

New methods have been developed for the design of a far ultraviolet multilayer reflection polarizer and retarder. A MgF2/Al/MgF2 three-layer structure deposited on a thick opaque Al film (substrate) is used for the design of polarizers and retarders. The induced transmission and absorption method is used for the design of a polarizer and layer-by-layer electric field calculation method is used for the design of a quarterwave retarder. In order to fabricate these designs in a conventional high vacuum chamber, we have to minimize the oxidation of the Al layers and somehow characterize the oxidized layer. X-ray photoelectron spectroscopy is used to investigate the amount and profile of oxidation. Depth profiling results and a seven layer oxidation model are presented.

Kim, Jongmin↗

Accounting for the photochemical variation in stratospheric NO2 in the SAGE III/ISS solar occultation retrieval

The Stratospheric Aerosol and Gas Experiment (SAGE) III has been operating on the International Space Station (ISS) since mid-2017. Nitrogen dioxide (NO2) number density profiles are routinely retrieved from SAGE III/ISS solar occultation measurements in the middle atmosphere. Although NO2 density varies throughout the day due to photochemistry, the standard SAGE NO2 retrieval algorithm neglects these variations along the instrument’s line of sight by assuming that the number density has a constant gradient within a given vertical layer of the atmosphere. This assumption will result in a retrieval bias for a species like NO2 that changes rapidly across the terminator. In this work we account for diurnal variations in retrievals of NO2 from the SAGE III/ISS measurements, and we determine the impact of this algorithm improvement on the resulting NO2 number densities. The first step in applying the diurnal correction is to use publicly available SAGE III/ISS products to convert the retrieved number density profiles to optical depth profiles. The retrieval is then re-performed with a new matrix that applies photochemical scale factors for each point along the line of sight according to the changing solar zenith angle. In general NO2 that is retrieved by accounting for these diurnal variations is more than 10% lower than the standard algorithm below 30 km. This effect is greatest in winter at high latitudes and generally greater for sunrise occultations than sunset. Comparisons with coincident profiles from the Optical Spectrograph and InfraRed Imager System (OSIRIS) show that NO2 from SAGE III/ISS is generally biased high; however the agreement improves by up to 20% in the mid-stratosphere when diurnal variations are accounted for in the retrieval. We conclude that diurnal variations along the SAGE III/ISS line of sight are an important term to consider for NO2 analyses at altitudes below 30 km.

Stratospheric NO2↗

In-situ measurement of the rate of U-235 fission induced by lunar neutrons

The depth profile of the neutron-induced fission rate of U-235 was directly measured to a depth of 350 g/sq cm by the Apollo 17 Lunar Neutron Probe Experiment. The fission rate rises sharply from the surface to a broad maximum from 110 to 160 g/sq cm and drops off at greater depths. The shape of the theoretical depth profile of Lingenfelter et al (1972) fits the measured capture rates well at all depths. The absolute magnitude of the experimental fission rates are (11 plus or minus 17)% lower than those calculated theoretically. The excellent agreement between theory and experiment implies that conclusions drawn previously by interpreting lunar sample data with the theoretical capture rates will not require revision. In particular, lunar surface processes, rather than uncertainties in the capture rates, are required to explain the relatively low neutron fluences observed for surface soil samples compared to the fluences expected for a uniformly mixed regolith.

Woolum, D. S.↗

Mass spectral molecular mapping shows benefits of thermal evaporation in prelithiated silicon-based electrodes

Silicon based composites have become increasingly popular as potential anodes for lithium-ion batteries due to their large storage capacity and potential ability to generate batteries with energy densities greater than 350 Wh kg −1 . These anodes often see reduced initial columbic efficiency (ICE) due to disruptive volume expansionup to 300% and continuous solid electrolyte interphase (SEI) layer formation. Prelithiation, where an excess reservoir of Li is added to the electrode to compensate for irreversible SEI formation losses during their sample preparation, has proven to solve the issue of immediate capacity loss. Thermal evaporation is a prelithiation technique with limited studies on its effectiveness. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to highlight the benefits of prelithiation via thermal evaporation. ToF-SIMS provides chemical mapping and spatial information in 2D and 3D visualizing the deposition of lithium, identifying Li x Si y alloy and Li x Si y O z silicate formation, and the distribution of lithium passivation into the electrodes. Passivation under different atmospheric conditions, such as inert Argon (Ar) and Ar/ carbon dioxide (CO 2 ), highlights the impact of the environment on the passivation effectiveness and formation of Li x Si y alloy and Li x Si y O z silicate. The ToF-SIMS molecular imaging and depth profiling results indicate that prelithiation via thermal evaporation effectively distributes lithium throughout the depth profile thickness of several hundred nanometers. It induces a greater degree of Li x Si y O z silicate formation over Li x Si y alloy. Our ToF-SIMS characterization results show the effectiveness of thermal evaporation in producing a more stable electrode and an electrode with an effective lithium reserve that can preserve its capacity.

Parker, Gabriel D. [Oak Ridge National Laboratory ↗

Exploration of LIBS as a novel and rapid elemental mapping technique of nuclear fuels in the form of surrogate TRISO particles

Laser-induced breakdown spectroscopy (LIBS) was employed to characterize coatings on surrogate fuel particles. Tri-structural isotropic (TRISO) particles are a proposed nuclear fuel alternative for high temperature reactors. These particles are constructed of a ZrO 2 kernel (as a surrogate to uranium), surrounded by an inner pyrolytic carbon layer and are surrounded by an outer carbide layer (ZrC, presented here) to act as a barrier to fission products generated during nuclear reactions. These particles are embedded within a graphite compact and housed within the reactor core. Simply put, due to their robust nature, performing elemental analysis of these particles poses a challenge. Presented here, LIBS is explored as a method for characterizing elemental constituents of these particles, with the focus being on rapid elemental mapping and depth profiling. Different from traditional elemental analysis techniques (e.g., inductively coupled plasma – based methods), LIBS is advantageous because it can directly analyze the sample surface and can detect light elements such as C and O, making it a viable technique for the analysis of small, multilayered particles as spatial elemental information is warranted in the production of these particles. In the work presented here, LIBS was successfully used for discerning small layers (30–50 μm), detecting the location of carbon and oxygen layers, providing fast 2-D mapping (<5 min per particle) and rapid depth profiling (10 s per particle).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Time of Flight Secondary Ion Mass Spectrometry for Characterization of Pt-Coated Porous Transport Layers in PEM Water Electrolyzers

Titanium-based porous transport layers (PTLs) and iridium-based catalyst layers (CLs) are two main components of proton exchange membrane water electrolyzers (PEMWEs). PTLs are typically coated with platinum to minimize interfacial losses and to support long-term operation. Optimizing coatings and the PTL-CL interface requires comprehensive characterization. This study establishes time-of-flight secondary ion mass spectrometry (ToF-SIMS) as a valuable technique for PTL characterization, addressing capabilities and limitations related to PTL morphology. A methodology was developed that uses a Cs + sputter beam for dynamic depth profiling, with data collected in both positive-ion (MCs + ) and negative-ion modes to generate depth profiles, 2D ion maps, and 3D ion reconstructions. ToF-SIMS detected relative differences in platinum-layer thickness between samples; these trends were validated by cross-sectional scanning transmission electron microscope (STEM) measurements and flat-titanium substrate controls. Interfacial oxide layers are identified in both ion modes, with enhanced oxide sensitivity in negative mode. The technique’s high sensitivity enables detection of nanometer-scale coatings and trace impurities within the bulk PTL structure. These results provide a methodological framework for analyzing Pt-coated PTLs, with the potential to extend to other components in PEMWEs and other electrolyzer systems.

36 MATERIALS SCIENCE↗

SALI chemical analysis of provided samples

SRI has completed the chemical analysis of all the samples supplied by NASA. The final batch of four samples consisted of: one inch diameter MgF2 mirror, control 1200-ID-FL3; one inch diameter neat resin, PMR-15, AO171-IV-55, half exposed and half unexposed; one inch diameter chromic acid anodized, EOIM-3 120-47 aluminum disc; and AO-exposed and unexposed samples of fullerene extract material in powdered form, pressed into In foil for analysis. Chemical analyses of the surfaces were performed by the surface analysis by laser ionization (SALI) method. The analyses emphasize surface contamination or general organic composition. SALI uses nonselective photoionization of sputtered or desorbed atoms and molecules above but close (approximately one mm) to the surface, followed by time-of-flight (TOF) mass spectrometry. In these studies, we used laser-induced desorption by 5-ns pulse-width 355-nm light (10-100 mJ/sq cm) and single-photon ionization (SPI) by coherent 118-nm radiation (at approximately 5 x 10(exp 5) W/sq cm). SPI was chosen primarily for its ability to obtain molecular information, whereas multiphoton ionization (not used in the present studies) is intended primarily for elemental and small molecule information. In addition to these four samples, the Au mirror (EOIM-3 200-11, sample four) was depth profiled again. Argon ion sputtering was used together with photoionization with intense 355-nm radiation (35-ps pulsewidths). Depth profiles are similar to those reported earlier, showing reproducibility. No chromium was found in the sample above noise level; its presence could at most be at the trace level. Somewhat more Ni appears to be present in the Au layer in the unexposed side, indicating thermal diffusion without chemical enhancement. The result of the presence of oxygen is apparently to tie-up/draw out the Ni as an oxide at the surface. The exposed region has a brownish tint appearance to the naked eye.

Becker, Christopher H.↗

Characterization of the Interfacial Orientation and Molecular Conformation in a Glass-Forming Organic Semiconductor

The ability to control structure in molecular glasses has enabled them to play a key role in modern technology; in particular, they are ubiquitous in organic light-emitting diodes. While the interplay between bulk structure and optoelectronic properties has been extensively investigated, few studies have examined molecular orientation near buried interfaces despite its critical role in emergent functionality. Direct, quantitative measurements of buried molecular orientation are inherently challenging, and many methods are insensitive to orientation in amorphous soft matter or lack the necessary spatial resolution. To overcome these challenges, we use polarized resonant soft X-ray reflectivity (pRSoXR) to measure nanometer-resolved, molecular orientation depth profiles of vapor-deposited thin films of an organic semiconductor Tris(4-carbazoyl-9-ylphenyl)amine (TCTA). Our depth profiling approach characterizes the vertical distribution of molecular orientation and reveals that molecules near the inorganic substrate and free surface have a different, nearly isotropic orientation compared to those of the anisotropic bulk. Comparison of pRSoXR results with near-edge X-ray absorption fine structure spectroscopy and optical spectroscopies reveals that TCTA molecules away from the interfaces are predominantly planar, which may contribute to their attractive charge transport qualities. Buried interfaces are further investigated in a TCTA bilayer (each layer deposited under separate conditions resulting in different orientations) in which we find a narrow interface between orientationally distinct layers extending across ≈1 nm. Coupling this result with molecular dynamics simulations provides additional insight into the formation of interfacial structure. This study characterizes the local molecular orientation at various types of buried interfaces in vapor-deposited glasses and provides a foundation for future studies to develop critical structure–function relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Depth-resolved carbon dioxide and methane concentrations in 522 lakes, ponds, and reservoirs worldwide

Lakes, ponds, and reservoirs (hereafter: “lakes”) are important sources of the greenhouse gases carbon dioxide (CO 2 ) and methane (CH 4 ). Emissions of CO 2 and CH 4 from lakes are regulated in part by in-lake processes, including the production and storage of gases in the lower parts of the water column (bottom waters). However, while substantial efforts have been made to improve estimates of greenhouse gas emissions from lakes, limited data on gas concentrations along depth profiles have prevented the incorporation of bottom-water processes in global emission estimates. Here, we present GHG-depths: the largest existing dataset of depth-profile CO 2 and CH 4 measurements worldwide, including 522 lakes across 38 countries and all seven continents. These data include contributions from 45 research teams and 56 published studies, totaling 2558 discrete sampling events. As global change continues to alter biogeochemical cycling in lakes, these data can help improve mechanistic models to better predict greenhouse gas production and emission from lakes worldwide.

Rabaey, Joseph S. [University of Minnesota, Duluth↗

Metagenome-assembled genomes from soil samples in control and warming plots in Blodgett Forest, CA (2014-2021)

The pathways of carbon transport and loss through and from soils—soil organic matter (SOM) depolymerization to dissolved organic carbon and mineralization to carbon dioxide (CO2)—are fundamentally driven by microbial activity, which is strongly regulated by environmental conditions. As part of LBNL (Lawrence Berkeley National Laboratory) TES (Terrestrial Ecosystem Science) Belowground Biogeochemistry Science Focus Area (SFA), we have established a novel whole-soil long-term warming experiment at the University of California (UC) Blodgett Forest Research Station (Sierra Nevada) in 2014, where we study the role of biogeochemical, microbial and geochemical process interactions in SOM decomposition and stabilization.Here, we present metagenome-assembled genomes (MAGs) for the bacterial and archaeal community from soil depth profiles collected from 2014 to 2021 from three paired control and warming plots. We collected soil samples across a range of depth profiles (spanning surface to 90 cm deep) from three paired control and warming plots from a temperate mixed forest in Northern California. Each paired plot had been subjected to experimental warming since June 2014 to simulate a predicted climate change scenario for northern California. 101 soil metagenomes were sequenced at JGI (Joint Genome Institute) and UCSF (University of California San Francisco) Center for Advanced Technology and can be found under the JGI (Joint Genome Institute) GOLD (Genomes Online Database) Sequencing project Gs0151586 and NCBI (National Center for Biotechnology Information) Projects PRJNA1225762 and PRJEB39497. Metagenomes were assembled using JGI (Joint Genome Institute) Metagenome Workflow (10.1128/mSystems.00804-20). For each metagenome, the assembled contigs were binned into genomes using 3 binning algorithms (cocacola, metabat, and maxbin) and the resulting bins were consolidated using dastool. The consolidated bins from all metagenomes were pooled, filtered by completeness (>50%) and contamination (<25%), and dereplicated at 99% ANI (average nucleotide identity) using dRep (https://github.com/MrOlm/drep).The dataset includes a zip file of 2321 MAG (Metagenome Assembled Genome) fasta files, the accession numbers for the underlying metagenomes, and a csv file with MAG (Metagenome Assembled Genome) quality metrics and taxonomic classification (GTDB -Genome Taxonomy Database-RS220). This dataset also includes a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata and a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type. A sample metadata file (samples.csv) that contains site information has also been included.

54 ENVIRONMENTAL SCIENCES↗

Solar flare proton spectrum averaged over the last 5000 years

The solar flare differential energy spectrum and integral proton flux above 10 MeV averaged over the last several thousand years are derived from thermoluminescence (TL) data. The dose-rate depth profile is obtained using a new TL equilibrium technique which is independent of the TL decay kinetics. The dose-rate depth profile produced by solar flare protons with a differential energy spectrum of the form dJ/dE = KE to the minus gamma power is calculated for arbitrary gamma. The best fit to the TL data in rock 14310 is obtained for gamma = 2.3 plus or minus 0.2 and an omnidirectional (4 pi) integral flux above 10 MeV of 40 to 80 prot/sq cm/sec. The TL half-life is determined to be 2000 yr. These results are compared to those for Na-22 (half-life of. 2.6 yr) and Al-26 (half-life of 740,000 yr) obtained by Wahlen et al. (1972) and Rancitelli et al. (1972), and it is concluded that the spectral shape and flux of protons in the interval from 25 to 100 MeV is the same within experimental errors when averaged over these three very different time periods.

Hoyt, H. P., Jr.↗

Measurement of proton production cross sections of (sup 10)Be and (sup 26)Al from elements found in lunar rocks

Cosmic rays penetrate the lunar surface and interact with the lunar rocks to produce both radionuclides and stable nuclides. Production depth profiles for long-lived radionuclides produce in lunar rocks are measured using Accelerator Mass Spectrometry (AMS). For a particular radionuclide these production depth profiles can be interpreted to give an estimate for the solar proton flux over a time period characterized by the half life of the radionuclide under study. This analysis is possible if and only if all the cross sections for the interactions of all cosmic ray particles with all elements found in lunar rocks are well known. In practice, the most important cross sections needed are the proton production cross sections, because 98% of solar cosmic rays and (similar to)87% of galactic cosmic rays are protons. The cross sections for the production of long-lived radionuclides were very difficult to measure before the development of AMS and only in recent years has significant progress been made in determining these essential cross sections. Oxygen and silicon are major constituents of lunar rocks. We have reported already C-14 production cross sections from O and Si for proton energies 25-500 MeV, and O(p,x)(sup 10)Be from 58 160 MeV[6]. Here we present new measurements for the cross sections O(p,x)Be-10,O(p,x)Be-7, Si(p,x)Be-7,Si(p,x)Al-26, and Si(p,x)Na-22 from approximately 30 - 500 MeV.

Sisterson, J. M.↗