SEARCH · Search NASA
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The National Laboratory of the Rockies (NLR) will conduct electrochemical testing and characterization on the partners lithium ion cells as well as provide and validate laser-ablated electrode materials for enhancing cell rate performance.
Currently, demand for rare earth elements (REEs) increased significantly. Coal is actively evaluated as potential economic sources for extraction of REEs. Here, in this work, laser-induced breakdown spectroscopy (LIBS) was evaluated for rapid estimation of REEs content and their distribution in the natural coal samples. The results were compared with similar laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) measurements. Thirteen coal samples (nine standard samples and five natural samples) were used in this study. Powder samples were pressed into pellets while coal chunks were directly ablated for data recording. Pellets of the powder standard samples were used to optimize the data acquisition system and then data recorded with this optimized system was used to identify the proper data acquisition and analysis models. After establishing the proper data acquisition system and analysis model using the standard samples, natural coal samples in powder form and their chunks were utilized to record LIBS and LA-ICP-MS spectra. Multivariate calibration models were developed using four of the natural samples, which were evaluated by predicting the REE content in the fifth sample. Principal component analysis was performed on the LIBS data obtained from the natural samples and it classified all the samples with high accuracy. Two-dimensional (2D) elemental mapping on coal chunk samples was also performed using both LIBS and LA-ICP-MS to study the distribution of REEs in the samples. The resulting elemental images and their correlations can be used to infer mineral distributions.
Conducting high resolution field microscopy with coupled laser spectroscopy that can be used to selectively analyze the surface chemistry of individual pixels in a scene is an enabling capability for next generation robotic and manned spaceflight missions, civil, and military applications. In the laboratory, we use a range of imaging and surface preparation tools that provide us with in-focus images, context imaging for identifying features that we want to investigate at high magnification, and surface-optical coupling that allows us to apply optical spectroscopic analysis techniques for analyzing surface chemistry particularly at high magnifications. The camera, hand lens, and microscope probe with scannable laser spectroscopy (CHAMP-SLS) is an imaging/spectroscopy instrument capable of imaging continuously from infinity down to high resolution microscopy (resolution of approx. 1 micron/pixel in a final camera format), the closer CHAMP-SLS is placed to a feature, the higher the resultant magnification. At hand lens to microscopic magnifications, the imaged scene can be selectively interrogated with point spectroscopic techniques such as Raman spectroscopy, microscopic Laser Induced Breakdown Spectroscopy (micro-LIBS), laser ablation mass-spectrometry, Fluorescence spectroscopy, and/or Reflectance spectroscopy. This paper summarizes the optical design, development, and testing of the CHAMP-SLS optics.
The uranium-containing molecules US 2 , OUS, and USe have been investigated using a pulsed laser ablation supersonic beam molecular source with time-of-flight mass spectrometric detection. Spectra have been recorded using the resonant two-photon ionization method over the spectroscopic range from 277 to 238 nm. These species have a myriad of excited electronic states in this spectroscopic region, leading to spectra that are highly congested and appear quasicontinuous. Sharp predissociation thresholds are observed, allowing precise bond dissociation energies to be measured. In the case of the triatomic molecules, it was necessary to use one laser for excitation and a delayed laser for ionization in order to observe a sharp predissociation threshold that allowed a precise bond dissociation energy to be measured. The resulting thermochemical values are D 0 (SU-S) = 4.910 ± 0.003 eV, D 0 (OU-S) = 5.035 ± 0.004 eV, and D 0 (USe) = 4.609 ± 0.009 eV. These results provide the first measurement of D 0 (USe) and reduce the error limits in the previous values of D 0 (SU-S) and D 0 (OU-S) by a factor of more than 70.
Over the past decades, crop yields have risen in parallel with increasing use of fossil-fuel derived nitrogen (N) fertilizers, but with concomitant negative impacts on climate and water resources. There is a need for more sustainable agricultural practices, and biological nitrogen fixation (BNF) could be part of the solution. A variety of nitrogen-fixing, epiphytic and endophytic plant growth promoting bacteria (PGPB) are known to stimulate plant growth. However, compared to the rhizobium-legume symbiosis, little mechanistic information is available as to how PGPB affect plant metabolism. Therefore, we investigated the metabolic changes in roots of the model grass species Setaria viridis upon endophytic colonization by Herbaspirillum seropedicae SmR1 (fix + ) or a fix - mutant strain (SmR54), compared to uninoculated roots. Endophytic colonization of the root is highly localized and, hence, analysis of whole root segments dilutes the metabolic signature of those few cells impacted by the bacteria. Therefore, we utilized in situ laser ablation electrospray ionization mass spectrometry (LAESI-MS) to sample only those root segments at or adjacent to the sites of bacterial colonization. We report netabolites involved in purine, zeatin, and riboflavin pathways were significantly more abundant in inoculated plants while metabolites indicative of nitrogen, starch, and sucrose metabolism were reduced in roots inoculated with the fix - strain or uninoculated, presumably due to N limitation. Interestingly, compounds, involved in indole-alkaloid biosynthesis were more abundant in the roots colonized by the fix - strain, perhaps reflecting a plant defense response.
The rhizosphere is a highly dynamic zone bridging plant roots with needed nutrient resources in soil. While the rhizosphere may be small, it has a disproportionally large impact on plant success and biomass production. A suite of rhizosphere-hosted microbial and geochemical interactions facilitate nutrient acquisition by plant roots, and, in turn, the roots stimulate these processes by supplying organic carbon into the rhizosphere. The small physical dimensions of the rhizosphere, however, can constrain efforts to elucidate key carbon exchange processes and their spatial extent and localization. We present a method for spatially resolved δ 13 C analysis of rhizosphere samples by coupling laser ablation (LA) sampling with isotopic analysis using capillary absorption spectroscopy (CAS) which differs from conventional mass spectrometer (MS) approaches. The CAS system has high sensitivity (requires fewer nanomoles of CO 2 per analysis) than comparable MS systems, which enables reduced sample size requirements to thereby improve spatial resolution (from 25 μm to as low as a projected 5 μm spatial resolution). We demonstrate the utility of CAS using rhizosphere samples from switchgrass plants exposed to 13 CO 2 . As a result, this technique will provide a capability for tracking the extent and spatial distribution of root exudate into the rhizosphere at highly detailed spatial scales.
Despite their importance in supplying nutrients, root traits related to maize domestication are scarce. We used laser ablation tomography to characterize the root architecture and anatomy of 5,300-y-old maize specimens recovered from San Marcos (Tehuacán, Mexico), revealing exquisite preservation of their cellular organization. Outer cortical cells contained thick and lignified walls typical of extant maize adapted to hard soils. By contrast, the absence of seminal roots is only found in the maize ancestor, teosinte. Two genes important for seminal root development had mutations that could relate to their absence. Our results indicate that some traits related to drought adaptation were not fully present in the earliest maize from Tehuacán, providing clues to conditions prevailing during early maize cultivation.
The synthesis of kinetically "frozen" metastable nanostructures remains elusive. This limitation has severely restricted the current paradigms in materials discovery. We overcame this challenge by phase-stabilizing unusually hyperoxidized and metastable amorphous aluminum oxide (a-AlO x ; 2.5 < x ≤ 3.5) nanostructures. Specifically, we employed laser ablation synthesis in solution (LASiS) as a one-pot nonequilibrium technique to achieve this pivotal advancement. Structural and compositional characterizations of the as-synthesized material reveal highly disordered a-AlO x nanoparticles that are remarkably stabilized by interfacial monolayers of ordered carbon atoms. Both structure and chemical composition were confirmed with disparate characterization methods at different length scales. The nanoparticles of sizes less than10 nm were stable even at elevated temperatures. Only at temperatures higher than 750 °C do the a-AlO x structures undergo a solid-solid phase transition that culminates in the formation of stable α-Al 2 O 3 while releasing excess trapped gases. In conclusion, such disruptive materials can find applications in emerging technologies seeking metastable phase-change materials for solid phase gas generators, batteries, neuromorphic computing, and energetic additives.
The mobility of plutonium (Pu) in the environment is affected by Pu–mineral interactions, such as adsorption–desorption and structural incorporation. Calcite (CaCO 3 ) is a common secondary phase in near surface environments and a major component of many rocks and soils and is expected to form as an alteration product of cement-based materials planned for use in geological repositories. The reactivity of the calcite surface and its ability to tolerate significant variations in its chemical composition through substitution of Ca for other cations make calcite a potentially important sink for environmental contaminants. Here, single crystals of calcite were synthesized from aqueous solutions in equilibrium with air containing Pu as either Pu(VI) or Pu(IV) and characterized using a combination of laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and X-ray absorption spectroscopy (XAS). These data are used to assess the amount, structure, and oxidation state of Pu co-precipitated into calcite, providing insight into the potential for Pu sequestration in calcite precipitates. Overall, the XAS and LA–ICP–MS data support the co-precipitation of plutonyl [Pu(VI/V)] in the bulk calcite, although the exact nature of the co-precipitated Pu complex is difficult to elucidate in the synthesized material. Co-precipitated plutonyl could be incorporated in either distorted Ca lattice sites or defect sites, and we provide evidence to suggest that Pu(VI) is reduced mainly to Pu(V) in the precipitated solid. LA–ICP–MS additionally shows that the co-precipitation of Pu(VI/V) is favored over the co-precipitation of Pu(IV). Altogether, our results suggest that Pu sequestration in calcite under environmental conditions could immobilize Pu and isolate it from groundwater interactions in contaminated environments.
In 2017, the Nuclear Forensics International Technical Working Group (ITWG) organized their fifth 37 Collaborative Materials Exercise (CMX-5). The exercise samples were two uranium dioxide fuel pellets 38 manufactured from the same starting materials by different processes to have similar bulk isotopic 39 composition, but different spatial uranium isotopic distributions. Sets of identical materials were sent to 40 all participating laboratories, who then utilized their existing nuclear forensic capabilities to 41 independently analyse fuel pellets and identify similarities and differences of the materials’ 42 characteristics. The analytical methods used to probe the fuel pellets included ex situ, such as sectioning 43 or breaking up the pellets and analyzing dissolved pieces using inductively coupled plasma mass 44 spectrometry (ICP-MS), analyzing particles collected from intact or fragmented pellets by secondary ion 45 mass spectrometry (SIMS), as well as in situ methods, such as laser ablation coupled with ICP-MS, 46 autoradiography and nanoSIMS. In this paper we present the results of these independent analyses and 47 compare the capabilities of those nuclear forensic analytical methods to uncover details of the isotopic 48 heterogeneity of uranium fuel pellets.
Rationale: Mass spectrometric measurement of the 230 Th/ 234 U ratio to calculate the purification age of enriched uranium is typically conducted via a combination of ion counters and faraday detectors, thus requiring an inter-detector calibration scheme. Here, our aim is to understand whether the pursuit of a simplified measurement scheme involving only faraday detectors is feasible. Methods: We investigate the possibility of determining U-Th model ages for two enriched uranium standards (NBL U630 and U850) by direct measurement of the 230 Th/ 234 U ratio (without chromatographic separation or isotope dilution) on a ThermoFisher Scientific Neoma MC-ICP-MS utilizing both solution and laser ablation (LA)-based sampling techniques and an all-faraday detector configuration. Results: For the solution mode analyses conducted on aliquots containing sub μg/mL total U, we produce composite average 230 Th/ 234 U model dates of May 19, 1988 (± 351 days), and March 26, 1961 (± 2.5 years) using the directly measured 230 Th/ 234 U ratios for the NBL U630 and U850 uranium standards, which have certified purification dates of June 6, 1988 (± 190 days), and December 31, 1957 (± 36.5 days), respectively. The ages produced by LA-based sampling of dried residues of the same standards deposited onto cotton TexWipes are less accurate and of poorer precision (June 23, 2004 ± 8.7 years for U630 and December 21, 1965 ± 7.9 years for U850) but still yield meaningful information in regards to the purification date. Conclusions: We believe that further refinement of the all faraday detector measurement approach to include development of a more robust Th/U relative sensitivity factor determination, signal cutoff selection, and data processing protocols will allow for this approach to be confidently applied to enriched uranium materials with unknown purification histories. Potential advantages of the method include the reduced sample handling and infrastructure requirements as well as the ability to simultaneously generate a broad picture of the uranium isotopic composition in tandem with the U-Th age determination.
In planetary exploration, in situ absolute geochronology is one of the main important measurements that needs to be accomplished. Until now, on Mars, the age of the surface is only determined by crater density counting, which gives relative ages. These ages can have a lot of uncertainty as they depend on many parameters. More than that, the curves must be ties to absolute ages. Thus far, only the lost lander Beagle 2 was designed to conduct absolute geochronology measurements, though some recent attempts using MSL Curiosity show that this investigation is feasible and should be strongly encouraged for future flight. Experimental: The Potassium (K)-Argon Laser Experiment (KArLE) is being developed at MSFC through the NASA Planetary Instrument Definition and Development Program (PIDDP). The goal of this experiment is to provide in situ geochronology based on the K-Ar method. A laser ablates a rock under high vacuum, creating a plasma which is sensed by an optical spectrometer to do Laser Induced Breakdown Spectroscopy (LIBS). The ablated material frees gases, including radiogenic 40Ar,which is measured by a mass spectrometer (MS). As the potassium is a content and the 40Ar is a quantity, the ablated mass needed in order to relate them. The mass is given by the product of the ablated volume by the density of this material. So we determine the mineralogy of the ablated material with the LIBS spectra and images and calculate its density. The volume of the pit is measured by using microscopy. LIBS measurement of K under high vacuum: Three independant projects [1, 2, 3] including KArLE, are developing geochronological instruments based on this LA-LIBS-MS method. Despite several differences in their setup, all of them have validated the methods with analyses and ages. However, they all described difficulties with the LIBS measurements of K [3,4]. At ambient pressure, the quantification of K by LIBS on geological materials can be accurate [5]. However the protocol of the LA-LIBS-MS experiment required hundreds of shots under high vacuum in order to free enough 40Ar* to be measured by the QMS. This long duration of ablation may induces significant changes in the LIBS spectra. The pressure may increases by orders of magnitudewithin the chamber and the laser pit geometry can change the effectiveness of ablation and intensity of plasma light received. These effects introduce variation between the first and last spectra and so the quantification of K is more complex. The ablation of one crater can give, depending on the protocol of acquisition, from tens to hundreds of spectra. Protocol and results: We are in the process of further characterizing the variation introduced into LIBS spectra by the use of hundreds of laser shots, and definining a protocol that can be used to ensure accuracy and reporoducibility in the results.We are using natural rock powder standards fused in a furnace, as well as mars analog samples with known K content. We will show the result of the calibration and some new statistical approaches in order to apprehend the effects of the long time ablation on rocks under high vacuum.
Co – Cu nanoparticles were obtained by pulsed laser ablation in a liquid medium in a constant magnetic field. The organic solvent, hexane, served as a liquid medium. The influence of the magnetic field on the formation of nanoparticles was studied. It is shown that the magnetic field leads to a decrease in the size distribution width of the resulting nanoparticles. (paper)
A high‐throughput, single‐source laser scribing method exploiting a transparent conducting oxide (TCO) indirect liftoff mechanism is developed to produce serially interconnected perovskite solar modules. The TCO‐based indirect liftoff mechanism relies solely on laser absorption in the front transparent electrode material reducing thermal damage to the overlying layers and allowing for fast scribing speeds with low‐cost μs‐pulse duration fiber laser systems. Minimal resistive power losses are observed with the method compared to conventional ablative laser scribes, maintaining the power conversion efficiencies of small‐area devices (≈0.2 cm 2 ) across significantly larger deposition areas (≈1 cm 2 ). Finally, demonstrating > 3 m s −1 processing speeds, TCO‐based liftoff provides the highest throughput laser scribing method for thin‐film photovoltaic devices produced on glass/TCO substrates, capable of processing large‐area perovskite solar modules at a manufacturing scale.
The project goal was to demonstrate new compact soft x-ray lasers emitting high energy ultrashort pulses at shorter wavelengths and increased repetition rates by amplification in atomic transitions in high density laser-created plasmas. To demonstrate these lasers we developed new high power solid state lasers. The project succeeded in demonstrating the shortest wavelength compact soft x-ray laser to date, 6.85 nm wavelength, and the highest repetition rate table-top soft x-ray laser, 400 Hz. We also applied these compact soft x-ray laser sources to determine the composition of materials with nanoscale resolution using a new technique that combines soft x-ray laser ablation with mass spectrometry, and we demonstrated that these lasers are capable of acquiring nanoscale resolution holograms with picosecond time resolution. The combination of an increased pumping efficiency with increased repetition rates can yield soft x-ray laser beams with an unprecedented average power on a table-top for applications demanding a high photon flux. We have demonstrated that the efficiency of plasma-based laser-pumped soft x-ray lasers can be significantly increased by detailed pulse shaping of the pump laser using a new pulse synthesizer. Results include the demonstration of 18.9 nm wavelength laser operation at a record 400 Hz repetition rate, and the extension of repetitive gain-saturated plasma-based table-top x-ray lasers to the shortest wavelength to date, 6.85 nm. Laser amplification was also observed at wavelengths as short at 5.8 nm by isolectronic scaling in Ni-like lanthanide ions. We have also conducted simulations to explore the possibility of demonstrating gain saturated atomic x-ray lasers near the carbon K-edge, in the “carbon window” for the first time. The work conducted under this program also includes the use of compact soft x-ray lasers in applications to problems of chemical interest, such as isotopic composition mapping of micron-size uranium particles with nanoscale resolution, and nanoscale resolution depth profiling analysis of CoNCN-coated electrodes for water oxidation catalysis. We also demonstrated single-shot high resolution soft x-ray Fourier transform holography over a broad 7 µm diameter field of view with ~ 5 ps temporal resolution.
Laser three-dimensional (3D) manufacturing technologies have gained substantial attention to fabricate 3D structured electrochemical rechargeable batteries. Laser 3D manufacturing techniques offer excellent 3D microstructure controllability, good design flexibility, process simplicity, and high energy and cost efficiencies, which are beneficial for rechargeable battery cell manufacturing. In this review, notable progress in development of the rechargeable battery cells via laser 3D manufacturing techniques is introduced and discussed. The basic concepts and remarkable achievements of four representative laser 3D manufacturing techniques such as selective laser sintering (or melting) techniques, direct laser writing for graphene-based electrodes, laser-induced forward transfer technique and laser ablation subtractive manufacturing are highlighted. Finally, major challenges and prospects of the laser 3D manufacturing technologies for battery cell manufacturing will be provided.
Mass and Raman spectrometers represent progressive analytical platforms for future in situ lander missions to explore the surface chemistry of planetary bodies across the Solar System. Europa, the Moon, and Mars are some of the primary targets for future NASA missions to search for extraterrestrial life and potentially habitable environments beyond Earth, further our understanding of the timing and formation of the Solar System and identify potentially viable economic resources such as water and/or valuable metal assets. The CORALS (Characterization of Ocean Residues And Life Signatures) and CRATER (Characterization of Regolith And Trace Economic Resources) instruments are UV laser-enabled OrbitrapTM mass spectrometers currently under development for prospective lander missions to Europa and the Moon, respectively. The Raman Mass Spectrometer (RAMS) is a dual wavelength (UV and visible) laser enabled hybrid instrument that incorporates laser desorption/ ionization mass spectrometry (LDMS) and micro-Raman microspectroscopy imaging (μRS) into a compact instrument package for multiple planetary missions to the inner and outer Solar System. The Pulse Laser Ablation Sampling and Mass Analysis (PLASMA) instrument combines a multi-wavelength laser (deep-UV to near-IR), plasma source, and collision cell with a heritage quadrupole mass spectrometer (QMS) to enable high precision trace element analyses for a future Lunar lander instrument. We report on the advancement of four compact, robust, and high technology readiness level (TRL) solid state lasers operating at wavelengths 213 nm, 266 nm, 515 nm, 532 nm and 1064 nm that serve as the sampling and ionization sources, for the CRATER, CORALS, RAMS and PLASMA investigations.
Large pieces of orbital debris form a significant risk of fragmentation in case of collision. Such fragmentation would greatly increase the number of trackable and untrackable debris on orbit. This makes them attractive targets for future rendezvous and disposal missions. However, these non-cooperative targets tend to be tumbling and rendezvous with them is a dangerous prospect. To avoid this danger, contactless detumbling through laser ablation has been proposed prior to rendezvous. Existing proposals for contactless laser-based detumbling have yet to include an in-depth study of the problem's guidance, navigation, and control requirements. In this work we develop an attitude and relative motion control scheme for a chaser satellite detumbling a non-cooperative target via laser. We show that detumbling can be achieved with reasonable time and dV budgets. With Monte Carlo methods we explore the impact of laser force on the detumbling operation and reveal some non-intuitive relationships.