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At least 577 records · Page 32

NASA Tech Briefs, September 2008

Topics covered include: Nanotip Carpets as Antireflection Surfaces; Nano-Engineered Catalysts for Direct Methanol Fuel Cells; Capillography of Mats of Nanofibers; Directed Growth of Carbon Nanotubes Across Gaps; High-Voltage, Asymmetric-Waveform Generator; Magic-T Junction Using Microstrip/Slotline Transitions; On-Wafer Measurement of a Silicon-Based CMOS VCO at 324 GHz; Group-III Nitride Field Emitters; HEMT Amplifiers and Equipment for their On-Wafer Testing; Thermal Spray Formation of Polymer Coatings; Improved Gas Filling and Sealing of an HC-PCF; Making More-Complex Molecules Using Superthermal Atom/Molecule Collisions; Nematic Cells for Digital Light Deflection; Improved Silica Aerogel Composite Materials; Microgravity, Mesh-Crawling Legged Robots; Advanced Active-Magnetic-Bearing Thrust- Measurement System; Thermally Actuated Hydraulic Pumps; A New, Highly Improved Two-Cycle Engine; Flexible Structural-Health-Monitoring Sheets; Alignment Pins for Assembling and Disassembling Structures; Purifying Nucleic Acids from Samples of Extremely Low Biomass; Adjustable-Viewing-Angle Endoscopic Tool for Skull Base and Brain Surgery; UV-Resistant Non-Spore-Forming Bacteria From Spacecraft-Assembly Facilities; Hard-X-Ray/Soft-Gamma-Ray Imaging Sensor Assembly for Astronomy; Simplified Modeling of Oxidation of Hydrocarbons; Near-Field Spectroscopy with Nanoparticles Deposited by AFM; Light Collimator and Monitor for a Spectroradiometer; Hyperspectral Fluorescence and Reflectance Imaging Instrument; Improving the Optical Quality Factor of the WGM Resonator; Ultra-Stable Beacon Source for Laboratory Testing of Optical Tracking; Transmissive Diffractive Optical Element Solar Concentrators; Delaying Trains of Short Light Pulses in WGM Resonators; Toward Better Modeling of Supercritical Turbulent Mixing; JPEG 2000 Encoding with Perceptual Distortion Control; Intelligent Integrated Health Management for a System of Systems; Delay Banking for Managing Air Traffic; and Spline-Based Smoothing of Airfoil Curvatures.

Source record↗

A Novel Approach to Simulate Realistic Concrete Microstructures under Irradiation

The concrete biological shield of light water reactors is exposed to high neutron and gamma irradiation doses in the long term. Irradiation deteriorates the physical and mechanical properties of concrete. Such effects need to be investigated to predict the concrete’s performance in the event of a lifetime extension of a nuclear power plant. This work combines high-resolution characterization techniques with fast-Fourier transform (FFT)-based 2-D simulations to evaluate the radiation-induced volumetric expansion (RIVE) and damage in concrete microstructures under neutron irradiation. Two concrete microstructures from samples provided by the Japan Concrete Aging Management Program (JCAMP) were characterized using micro x-ray fluorescence (mXRF) to obtain elemental intensity maps, and energy-dispersive x-ray spectroscopy to complement mXRF with local elemental information for Na. Minerals and cement paste are then identified based on the elemental composition to produce high-resolution phase maps, resulting in a more accurate representation of the microstructures compared to previous work. Simulations of radiation-induced volumetric expansion (RIVE), creep, and damage in JCAMP concrete use the fast Fourier transform (FFT)-based code Microstructure Oriented Scientific Analysis of Irradiated Concrete (MOSAIC) combined with the irradiated minerals, aggregates, and concrete (IMAC) database, which contains mineral-specific RIVE models. Overall, the simulation results are in fair agreement with experimental data.

Cheniour, Amani↗

Ultrafast Laser Welding and Terahertz Time-domain Spectroscopy of Soda Lime Silicate Glass

Joining and welding techniques of similar and dissimilar materials have reached their limits due to the inflexibility of adapting dielectric materials, e.g., glasses and ceramics, reproducibility for transparent materials, and cycle process time. The ability to join pieces of glasses using laser irradiation allows rapid processing of vacuum insulating glass (VIG) for a widening range of commercial energy-efficient applications. We have used a 1064-nm laser wavelength with 15 picoseconds pulse width and a 155-kHz repetition rate to weld commercial plate glass pieces. The welded samples were characterized via x-ray fluorescence (XRF), time-of-flight secondary ion mass spectrometry (TOF–SIMS), polarimetry, and terahertz time-domain spectroscopy (THz-TDS) to determine the integrity of the weld and chemical changes in the welded areas. Our data shows no significant changes in glass chemistry and structure on average over nano- to micro-scales occurred from the welding process within the limits of the characterization tools. Our results demonstrate successful welding of glass plates without significant changes in the glass chemistry, structure, or properties in the laser-modified region or strains in the bulk glass.

Matthies, Kathleen [ORNL] (ORCID:0009000213135441)↗

Spectroscopic investigation of historical uranium glasses

Here, we present spectroscopic investigations of uranium in two historical glasses. A 1920's-1930's Art Deco (Bagley Carnival) green soda-lime-silica uranium glass bowl and a 1930's-1940's (Thomas Webb) yellow full lead crystal uranium glass vase were studied using optical absorption spectroscopy, XRF and SEM-EDX, X-band EPR and High- Energy Resolution Fluorescence-Detected (HERFD)-XANES. Uranium speciation may be different in the two glasses. Uranium occurs as uranyl groups (UO 2 2+ ) with minority reduced uranium species, mostly as U(V), more important in the Webb glass than in the Bagley glass. The differences between the two glasses arise from the fining procedure and result from the presence of other multivalent elements and differences in base glass composition. Electron Paramagnetic Resonance (EPR) spectra show the presence of an incipient signal close to g~2, partially annealed by heating to 550 °C, which we assign to a small concentration of radiation-induced defects caused by uranium decay. The presence of multivalent glass components in addition to U (As + Cu + Fe in the Bagley glass and Sb + Fe in the Webb glass) can trap the electron-hole pairs generated by the presence of uranium. This may explain the weakness of this signal in these glasses that anyway received a limited radiation dose since their fabrication. The low activity of these glasses, close to the background radiation, confirms that there is no danger to exhibiting them in museums.

36 MATERIALS SCIENCE↗

Finding a needle in a haystack: quantitative HERFD-XRF imaging and HERFD-XANES characterization of trace platinum in gold solidi from the Late Roman and Byzantine Empires

High-Energy Resolution Fluorescence Detection X-Ray Fluorescence (HERFD-XRF) imaging and HERFD X-ray Absorption Near Edge Structure (XANES) spectroscopy are used to quantify and characterize trace platinum (Pt) in gold solidi from the Late Roman and Byzantine Empires. Historically, the elemental analysis of coins has been pivotal in distinguishing authentic artifacts from forgeries, elucidating minting practices, and understanding economic shifts. Notably, a new gold source with high platinum content appeared in the fourth century CE, transforming the Roman economy. Traditional methods struggled to detect platinum due to the overwhelming gold matrix. Here, this study demonstrates the effectiveness of HERFD techniques in resolving this challenge. Three gold solidi, minted between 654 and 659 CE, were analyzed alongside reference gold materials with known Pt concentrations. The HERFD-XRF imaging revealed spatial distributions of platinum, highlighting non-uniformities within the coins. Additionally, HERFD-XANES spectroscopy identified the oxidation states and chemical speciation of platinum. Results demonstrate that platinum in the solidi primarily exists as metallic Pt, with some surface oxidation. The findings align with previous measurements but reveal higher Pt concentrations and significant inhomogeneities. This research confirms the reliability of HERFD methods for quantifying trace elements and provides new insights into the raw material sources and minting techniques of ancient gold coins. The non-destructive nature of this approach allows for extensive analyses, offering valuable data for historical, economic, and archaeological studies. This innovative application of HERFD-XRF imaging and XANES in cultural heritage research underscores the potential for detailed material characterization and conservation, enhancing our understanding of ancient economies and trade patterns.

Van Loon, Lisa L.↗

Nonintrusive spectroscopic techniques for supersonic/hypersonic aerodynamics and combustion diagnostics

This paper presents an overview of the primary nonintrusive diagnostic techniques being developed by the NASA Langley Research Center to address the validation needs of Computational Fluid Dynamic (CFD) codes. The techniques include absorption in the UV and IR, Laser Induced Fluorescence, electron beam fluorescence, and a number of scattering techniques including Rayleigh, spontaneous Raman, and several coherent Raman spectroscopies. Most of the techniques are highly specialized, require complex data interpretation, and can satisfy only a few of the CFD needs. For these reasons, the evolving trend in flowfield diagnostics appears to favor a mode in which the diagnostic researcher, the experimental aerodynamicist, and the CFD community jointly define experiments based on the aeronautical requirements and on available diagnostic techniques.

Exton, R. J.↗

Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

Wine, Paul H.↗

Characterization of Potential Micrometeorites by Synchrotron Analysis

Micrometeorites (MMs) are small particles that account for most of the extraterrestrial material deposited on Earth. Synchrotron X-ray fluorescence and diffraction allowed for chemical and mineral characterization to distinguish MM from atmospheric particulate. The relative components of iron, nickel, and other elements were considered in the identification of ferrous MM while high amounts of titanium were considered an indication that the particles were of atmospheric origin. Out of 100 samples collected by high school students and teachers, eight were taken to a synchrotron for analysis. Of those eight, three exhibited extraterrestrial compositions. X-ray absorption near-edge structure analysis revealed that the same three samples contained sulfide, the main sulfur form constituent in MM. X-ray microdiffraction analysis showed the presence of the minerals pentlandite and forsterite. Collectively, these results support the extraterrestrial nature of the three particles.

58 GEOSCIENCES↗

Autonomous sputter synthesis of thin film nitrides with composition controlled by Bayesian optimization of optical plasma emission

Autonomous experimentation has emerged as an efficient approach to accelerate the pace of material discovery. Although instruments for autonomous synthesis have become popular in molecular and polymer science, solution processing of hybrid materials, and nanoparticles, examples of autonomous tools for physical vapor deposition are scarce yet important for the semiconductor industry. Here, we report the design and implementation of an autonomous workflow for sputter deposition of thin films with controlled composition, leveraging a highly automated sputtering reactor custom-controlled by Python, optical emission spectroscopy (OES), and a Bayesian optimization algorithm. We modeled film composition, measured by x-ray fluorescence, as a linear function of plasma emission lines monitored during co-sputtering from elemental Zn and Ti targets in an N 2 and Ar atmosphere. A Bayesian control algorithm, informed by OES, navigates the space of sputtering power to fabricate films with user-defined compositions by minimizing the absolute error between desired and measured optical emission signals. We validated our approach by autonomously fabricating Zn x Ti 1-x N y films that deviate from the targeted cation composition by a relative ±3.5%, even for 15 nm thin films, demonstrating that the proposed approach can reliably synthesize thin films with a specific composition and minimal human interference. Moreover, the proposed method can be extended to more difficult synthesis experiments where plasma intensity lines depend non-linearly on pressure, or the elemental sticking coefficients strongly depend on the substrate temperature.

36 MATERIALS SCIENCE↗

Metallized Capillaries as Probes for Raman Spectroscopy

A class of miniature probes has been proposed to supplant the fiber-optic probes used heretofore in some Raman and fluorescence spectroscopic systems. A probe according to the proposal would include a capillary tube coated with metal on its inside to make it reflective. A microlens would be hermetically sealed onto one end of the tube. A spectroscopic probe head would contain a single such probe, which would both deliver laser light to a sample and collect Raman or fluorescent light emitted by the sample.

Pelletier, Michael↗

Single-Determinant Ground State in Ce 4+ Imidophosphorane Complexes

X-ray spectroscopy techniques are critical in the electronic structure analysis of high-valent lanthanides. The interpretation of multipeaked features at the lanthanide L 3 -edge has remained a challenging question, as it is observed across a range of material classes. A series of structurally related Ce 4+ complexes were prepared to probe the potential ligand field perturbation of the ground state within the series. The tuning of relative 4f and ligand orbital energies in homoleptic and heteroleptic tetravalent Ce imidophosphorane complexes is achieved through ligand derivatization and is clearly demonstrated by UV−vis spectroscopy and electrochemically measured redox potentials. However, Ce L 3 - edge high-energy resolution fluorescence-detected (HERFD) X-ray absorption near-edge structure (XANES) spectra present features at consistent numbers and energies across the range of complexes. Resonant inelastic X-ray scattering (RIXS) is employed to visualize the observed features in the HERFD-XANES spectra. Large complete active space configuration interaction singles and doubles (CASCISD) calculations demonstrate that the ground-state wave function of all complexes can be described employing a single determinant. As a result, the multielectron feature at the L 3 -edge observed in this study for the Ce 4+ imidophosphorane complexes is described as excited-state multiconfigurational behavior that is independent of ligand variation, in systems where the ground state is described using the simple single determinant wave function.

Lanthanides↗

Discovery of Soft Spectral Component and Transient 22.7s Quasi Periodic Oscillations of SAX J2103.5+4545

XMM-Newton observed SAX J2103.5+4545 on January 6, 2003, while RXTE was monitoring the source. Using RXTE-PCA dataset between December 3, 2002 and January 29, 2003, the spin period and average spin-up rate during the XMM-Newton observations were found to be 354.7940+/-0.0008 s and (7.4 +/- 0.9) x 10(exp -13) Hz/s respectively. In the power spectrum of the 0.9-11 keV EPIC-PN lightcurve, we found quasi periodic oscillations around 0.044 Hz (22.7 s) with an rms fractional amplitude approx. 6.6 %. We interpreted this QPO feature as the Keplerian motion of inhomogeneities through the inner disk. In the X-ray spectrum, in addition to the power law component with high energy cutoff and approx. 6.4 keV fluorescent iron emission line, we discovered a soft component consistent with a blackbody emission with kT approx. 1.9 keV. The pulse phase spectroscopy of the source revealed that the blackbody flux peaked at the peak of the pulse with an emission radius approx. 0.3 km, suggesting the polar cap on the neutron star approx. 6.42 keV was shown to peak at the off-pulse phase, supporting the idea that this feature arises from fluorescent emission of the circumstellar material around the neutron star rather than the hot region in the vicinity of the neutron star polar cap.

Inam, S. C.↗

Carrier gradients and the role of charge selective contacts in lateral heterojunction all back contact perovskite solar cells

Realizing photovoltaic devices that achieve the full potential of the metal halide perovskite material will require improved insight regarding the role of selective contacts and how key interfaces operate when mobile defects are present. However, measuring interface properties in typical device stacks where the perovskite layer is thin and sandwiched between two contacts has been a challenge. Here, we fabricate p-i-n and p-n lateral heterojunctions with nickel oxide/titanium oxide all back contacts, permitting us to employ a comprehensive analysis approach, including ultraviolet and X-ray photoemission spectroscopy (UPS/XPS), angle-resolved X-ray absorption spectroscopy (XAS), Kelvin probe force microscopy (KPFM), surface photovoltage (SPV), hyperspectral imaging (HSI), and time-resolved fluorescence lifetime imaging microscopy (TR-FLIM) to discern the role of selective contacts. Specifically, we tune the selectivity of the contacts, changing the gradient in the carrier concentration across the surface of the active layer, which is connected to carrier extraction at the buried interface, and thus the device functionality.

25 ENERGY STORAGE↗

Advanced Non-Intrusive Instrumentation for Propulsion Engines

Changes in engine technology such as higher temperatures, higher tip speeds, new metal/composite/ceramic materials together with radical changes in design philosophy will require amongst other prerequisites the ability to measure and to monitor key internal gas and structural characteristics. The symposium papers presented non-intrusive measurement and analysis technologies in the following categories: Laser Point Measurements (11); Absorption and Infrared Techniques (4); Paints - Surface Sensors (6); Laser Induced Fluorescence (6); Mechanical (7); Films (5); Laser Planar Measurement (9); and a Keynote Address.

Propulsion↗

Altered excitation energy transfer between phycobilisome and photosystems in the absence of ApcG, a small linker peptide, in Synechocystis sp. PCC 6803, a cyanobacterium

Phycobilisome (PBS) is a large pigment-protein complex in cyanobacteria and red algae responsible for capturing sunlight and transferring its energy to photosystems (PS). Spectroscopic and structural properties of various PBSs have been widely studied, however, the nature of so-called complex-complex interactions between PBS and PSs remains much less explored. In this work, we have investigated the function of a newly identified PBS linker protein, ApcG, some domain of which, together with a loop region (PB-loop in ApcE), is possibly located near the PBS-PS interface. Using Synechocystis sp. PCC 6803, we generated an ApcG deletion mutant and probed its deletion effect on the energetic coupling between PBS and photosystems. Steady-state and time-resolved spectroscopic characterization of the purified ΔApcG-PBS demonstrated that ApcG removal weakly affects the photophysical properties of PBS that the spectroscopic properties of terminal energy emitters are comparable to those of PBS from wild-type. However, analysis of fluorescence decay imaging datasets reveals that ApcG deletion induces disruptions within the allophycocyanin (APC) core, resulting in the emergence (splitting) of two spectrally diverse subgroups with some short-lived APC. Profound spectroscopic changes of the whole ΔApcG mutant cell, however, emerge during state transition, a dynamic process of light scheme adaptation. The mutant cells in State I show a substantial increase in PBS-related fluorescence. On the other hand, global analysis of time-resolved fluorescence demonstrates that in general ApcG deletion does not alter or inhibit state transitions if it is interpreted only in terms of the changes of the PSII and PSI fluorescence emission intensity. Furthermore, the results revealed yet–to–be discovered mechanism of ApcG-docking induced excitation energy transfer regulation within PBS or to Photosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Correlative Surface Imaging Reveals Chemical Signatures for Bacterial Hotspots on Plant Roots

The rhizosphere is arguably the most complex microbial habitat on earth, comprising an integrated network of plant roots, soil and a highly diverse microbial community (the rhizosphere microbiome)1. Understanding, predicting and controlling plant-microbe interactions in the rhizosphere will allow us to harness the plant microbiome as a means to increase or restore plant ecosystem productivity, improve plant responses to a wide range of environmental perturbations, and mitigate effects of climate change by designing ecosystems for long-term soil carbon storage1. To this end, it is imperative to develop new molecular approaches with high spatial resolution to capture interactions at the plant-microbe, microbe-microbe, and plant-plant interfaces. In this work, we designed an imaging sample holder that allows integrated surface imaging tools to map the same locations of a plant root-microbe interface with submicron lateral resolutions, providing novel in vivo analysis of root-microbe interactions. Specifically, confocal fluorescence microscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM) were used for the first time for correlative imaging of the Brachypodium distachyon root and its interaction with Pseudomonas SW25, a typical plant growth-promoting soil bacterium. Imaging data suggest that the root surface is inhomogeneous and that the interaction between Pseudomonas and Brachypodium roots was confined to only few spots along the sampled root segments and that the bacterial attachment spots were enriched in Na- and S-related and high-mass organic species. We conclude that attachment of the Pseudomonas cells to the root surface is outcompeted by strong root-soil mineral interactions but facilitated by formation of extracellular polymeric substances (EPS).

Plant root, Plant growth-promoting bacteria, soil,↗