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At least 1,153 records · Page 64
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Atmospheric ice nuclei concentration measurements over a high altitude-station in the Western Ghats, India

Mixed-phase and ice clouds play a significant role in modulating the Indian summer monsoon rainfall, and modeling studies suggest that inaccurate representation of ice nucleating particles (INP) is one of the factors, which have resulted in a deficiency in the prediction of cloud properties and hydrological cycle. We do not understand the ice nucleation mechanisms to represent the ice formation in the model, and therefore more INP measurements at various supercooled temperatures are needed. This study reports for the first time real-time INP concentration at a high altitude station in the Western Ghats region of India, and these results will be used to constrain the ice nucleation parameterizations in the model. The variation of INP for any particular cloud condition can have strong microphysical responses of mixed-phase precipitation formation processes. Also, to improve the representation of heterogeneous ice nucleation, INP measurements of various types of aerosols commonly observed over the Indian region are needed. This study presents, the INP concentrations and daily concentration of non-refractory chemical composition (organics, sulfate, nitrate, ammonium, and chloride), cloud condensation nuclei (CCN), and aerosol size distribution. Spectrometer for Ice Nuclei (SPIN) was operated to measure INP concentration at the mountain site from August to December 2018. INP measurements were performed at three different temperatures (-25, -30, and - 34 °C) in the immersion freezing mode relevant for mixed-phase cloud conditions. The average INP concentrations approximately varied from 0.18 to 12.4 L-1, 0.39 to 24 L-1, 1.1 to 40.2 L-1 at -25, -30, and - 34 °C, respectively. These concentrations are within the concentrations reported in the literature from different regions across the globe. The air mass back trajectory analysis showed that continental air mass contains more INP compared to maritime air mass. The information on INP concentration and chemical characteristics of aerosol will help to improve heterogeneous ice nucleation parameterization in numerical models.

Kumar, Anil V.↗
NASA NTRS2006

Semiautonomous Avionics-and-Sensors System for a UAV

Unmanned Aerial Vehicles (UAVs) autonomous or remotely controlled pilotless aircraft have been recently thrust into the spotlight for military applications, for homeland security, and as test beds for research. In addition to these functions, there are many space applications in which lightweight, inexpensive, small UAVS can be used e.g., to determine the chemical composition and other qualities of the atmospheres of remote planets. Moreover, on Earth, such UAVs can be used to obtain information about weather in various regions; in particular, they can be used to analyze wide-band acoustic signals to aid in determining the complex dynamics of movement of hurricanes. The Advanced Sensors and Electronics group at Langley Research Center has developed an inexpensive, small, integrated avionics-and-sensors system to be installed in a UAV that serves two purposes. The first purpose is to provide flight data to an AI (Artificial Intelligence) controller as part of an autonomous flight-control system. The second purpose is to store data from a subsystem of distributed MEMS (microelectromechanical systems) sensors. Examples of these MEMS sensors include humidity, temperature, and acoustic sensors, plus chemical sensors for detecting various vapors and other gases in the environment. The critical sensors used for flight control are a differential- pressure sensor that is part of an apparatus for determining airspeed, an absolute-pressure sensor for determining altitude, three orthogonal accelerometers for determining tilt and acceleration, and three orthogonal angular-rate detectors (gyroscopes). By using these eight sensors, it is possible to determine the orientation, height, speed, and rates of roll, pitch, and yaw of the UAV. This avionics-and-sensors system is shown in the figure. During the last few years, there has been rapid growth and advancement in the technological disciplines of MEMS, of onboard artificial-intelligence systems, and of smaller, faster, and smarter wireless telemetry systems. The major attraction of MEMS lies in orders-of-magnitude reductions of power requirements relative to traditional electronic components that perform equivalent functions. In addition, the compactness of MEMS, relative to functionally equivalent traditional electronics systems, makes MEMS attractive for UAV applications. Recent advances in MEMS have made it possible to produce pressure, acceleration, humidity, and temperature sensors having masses in subgram range and possessing sensitivities and accuracies comparable to those of larger devices.

Shams, Qamar↗
DOE OSTI2025

Thermodynamic modeling of countercurrent chemical looping reverse water gas shift process for redox material screening

The reverse water gas shift (RWGS) reaction is a key pathway for CO 2 utilization, particularly within Power-to-X process chains aimed at sustainable fuel and chemical production. Countercurrent chemical looping (CL-RWGS) using non-stoichiometric oxides can overcome equilibrium limitations of conventional RWGS reactors, enabling significantly higher CO 2 conversions. However, modeling the limiting performance of such systems is challenging due to their multiphase nature and coupled spatial and temporal variation in chemical composition. In this work, we present a discretized batch equilibrium model that simulates CL-RWGS reactors as a series of localized equilibrium exchanges between gas and solid elements. The model is numerically stable, computationally efficient, and free of kinetic source terms, making it well-suited for parametric studies and system-level integration. It is validated against established convection–diffusion models and shown to predict reasonable upper bounds on experimental results. Application of the model to a range of oxygen carrier materials identifies cerium–zirconium solid solutions, particularly Ce 0.80 Zr 0.20 O 2 , as a promising class offering superior oxygen storage characteristics compared to state-of-the-art La 0.6 Sr 0.4 FeO 3 . This framework provides a robust platform for materials screening, reactor sizing, and performance optimization in chemical looping systems. The model implementation is available as open-source software to support further research and development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

High-Pressure Synthesis of Metal-Ceramic Nano-Composites

The major problems in fabrication of nano-crystal line materials form nano-powders are: (1), coarsening of the initial nano-size grains, (2), insufficient densification (high concentration of pores), and, (3), conversion of diamond into graphite (for diamond-based ceramics). We have developed a novel technique of the synthesis of nano-composite materials applying very high (up to about 10 GPa) pressures. In this technique, one component is pre-compacted and placed next to another having a lower melting point temperature. The whole sample is pressed and the temperature raised above the melting point of the second component, what results in the melt getting pressed into the (nano-size) pores of the compact. Upon subsequent crystallization the melt forms the second nanophase. The process is fast, on the order of seconds, and the temperatures are relatively low what prevents, or at least significantly reduces coarsening of the starting nanophase grains. Also, conversion of diamond into graphite can be prevented. The technique allows for control of the final product properties through a proper selection of (1) the initial compact density and grain size, (2) chemical composition of the source, and (3) the temperature and pressure of the process. The application of the technique to the synthesis of SiC and diamond with Si, Ge, and different metals. Results of the in-situ investigation of the synthesis process by synchrotron X-ray diffraction technique will be presented.

Gierlotka, S.↗
DOE OSTI2026

Synthesis and Properties of Bulk Mg 3 WN 4 in a Wurtzite-Derived Structure

Experimental synthesis of theoretically predicted materials with controlled elemental coordination environments can lead to the realization of useful properties, such as facile ion transport or ferroelectric switching. Among such materials are ternary nitrides in the Mg−W−N composition space, where several stable and metastable compounds have been predicted and synthesized recently in bulk and film forms. Here, we report for the first time on the bulk synthesis of Mg 3 WN 4 in a wurtzite-derived crystal structure via a solid-state metathesis reaction. In situ synchrotron powder X-ray diffraction shows how the ion exchange proceeds from Li 6 WN 4 + MgCl 2 precursors to Mg 3 WN 4 + LiCl products, with the reaction starting slowly near 380 °C and completing by 600 °C, including the presence of a competing disordered rocksalt-derived phase (Mg,W)N above 440 °C. The follow-up ex situ powder synthesis at 400 °C for 0.5 h with 10% excess MgCl 2 reveals the cation-ordered nature of the wurtzite-derived Mg 3 WN 4 structure with polar symmetry confirmed by second-harmonic generation measurements. Optical absorption spectra, chemical composition analysis, and electron microscopy imaging suggest that bulk Mg 3 WN 4 obtained via metathesis reaction is prone to defect formation. Overall, this study shows that selective ex situ synthesis of the phase-pure ternary nitrides, informed by in situ measurements, is possible by carefully controlling the thermal budget of the reaction and paves the way toward property characterization of the Mg 3 WN 4 wurtzite-derived material.

36 MATERIALS SCIENCE↗
NASA NTRS2002

Microfossils in the Murchison and Rainbow Carbonaceous Meteorites

Astrobiologists are working to develop methodologies for the recognition of bacterial microfossils, biominerals, and chemical biomarkers in terrestrial rocks, to provide a basis for the scientific assessment of possible microfossils in meteorites and other Astromaterials. During the past 5 years, we have conducted electron microscopy investigations to understand the morphology and chemical composition of microfossils in ancient terrestrial rocks and to search for microfossils presence in meteorites. We have detected evidence of indigenous microfossils and biominerals in-situ in every carbonaceous meteorite investigated but have found no evidence for microfossils in the nickel-iron and stony meteorites studied. In this paper, we provide a brief review of prior evidence for microfossils in meteorites and present Scanning and Environmental Scanning Electron Microscope (SEM and ESEM) and Field Emission Scanning Electron Microscope (FESEM) images of microfossils found in-situ in freshly fractured surfaces of the Murchison and Rainbow meteorites. We describe the techniques and methods used to protect the samples from contamination and for the discrimination of indigenous microfossils from recent terrestrial contaminants We provide data from Energy Dispersive Spectroscopy (EDS) and Link microprobe analysis of the chemical elements and 2D x-ray maps as strong evidence that these biogenic forms are indigenous to the meteorites and cannot logically be interpreted as recent bio-contaminants. We show evidence of framboidal magnetites and pyrites and compare them with framboidal magnetites and pyrites found in Cambrian richs from the Siberian Platform.

Hoover, Richard B.↗
DOE OSTI2025

Application of Electrochemical Methods to Molten Salt Reactors: Draft TLR Documenting Assessment of Electrochemical Monitoring

Nuclear Regulatory Commission (NRC) is developing the regulatory framework and technical expertise to support regulatory review of advanced non-water reactors, including molten salt reactors (MSRs). In an MSR, it is essential that the salt chemistry be maintained in a desired range in terms of redox potential for reliable operation and mitigation of corrosion to structural materials in the reactor, particularly the reactor vessel and heater exchanger. Measuring the redox potential of the salt in the reactor would also allow for the material lifetimes to be predicted more accurately, and chemical issues to be diagnosed more quickly. In addition to the chemical composition analysis by ICP-MS, electrochemical methods including potentiometry and linear wave scanning (LSC) were also used in molten salt reactor experiment (MSRE) for redox potential monitoring purposes. Electrochemcial methods offers unique advantages such as quick turnaround in results and unique capability of in-line monitoring of redox potential, and are considered popular electroanalytical techniques that can be used to monitor redox potentials and salt chemistry including impurities. The last two decades have seen significant advances in science and engineering of electrochemical methods for potential application to molten salts. The primary goal of this report is to assist NRC in understanding the monitoring of the salt chemistry by electrochemical methods and provide NRC reviewers with necessary information and tools to support regulatory review of MSR designs. This reports consists of two majors parts—Part 1, chemical potential of molten salts and effects by fission process in MSR; Part 2, assessment of electrochemical methods for application to MSRs. The TRLs of the typical relevant electrochemical methods for molten salts were evaluated based on the DOE TRL guidelines and upon a review of the current status of the electrochemical methods for two typical salt systems, fluoride and chloride, for MSRs.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1972

Relativistic heavy cosmic rays

During three balloon flights of a 1 sq m sr ionization chamber/Cerenkov counter detector system, measurements were made of the atmospheric attenuation, flux, and charge composition of cosmic ray nuclei with 16 is less than or = Z is less than or = 30 and rigidity greater than 4.5 GV. The attenuation mean free path in air of VH (20 less than or = Z less than or = 30) nuclei is found to be 19.7 + or - 1.6 g/sq cm, a value somewhat greater than the best previous measurement. The attenuation mean free path of iron is found to be 15.6 + or - 2.2 g/sq cm, consistent with predictions of geometric cross-section formulae. An absolute flux of VH nuclei 10 to 20% higher than earlier experiments at similar geomagnetic cutoff and level of solar activity was measured. The relative abundances of even-charged nuclei are found to be in good agreement with results of other recent high resolution counter experiments. The observed cosmic ray chemical composition implies relative abundances at the cosmic ray source of Ca/Fe = 0.12 + or - 0.04 and S/Fe = 0.14 + or - 0.05.

Mewaldt, R. A.↗
NASA NTRS2020

Using Simulated Micrometeoroid Impacts to Understand the Progressive Space Weathering of the Surface of Mercury

The surfaces of airless bodies such as Mercury are continually modified by space weathering, which is driven by micrometeoroid impacts and solar wind irradiation. Space weathering alters the chemical composition, microstructure, and spectral properties of surface regolith. In lunar and ordinarychondritic style space weathering, these processes affect the reflectance properties by darkening (lowering of reflectance), reddening (increasing reflectance with increasing wavelength), and attenuation of characteristic absorption features. These optical changes are driven by the production of nanophase Febearing particles (npFe). While our understanding of these alteration processes has largely been based on data from the Moon and near-Earth S-type asteroids, the space weathering environment at Mercury is much more extreme. The surface of Mercury experiences a more intense solar wind flux and higher velocity micrometeoroid impacts than its planetary counterparts at 1 AU. Additionally, the composition of Mercury’s surface varies significantly from that of the Moon. Most notably, a very low albedo unit has been identified on Mercury’s surface, known as the low reflectance material (LRM). This unit is enriched with up to 4 wt.% carbon, likely in the form of graphite, over the local mean. In addition, the surface concentration of Fe across Mercury’s surface is low (<2 wt.%) compared to the Moon. Our understanding of how these low-Fe and carbon phases are altered as a result of space weathering processes is limited. Since Fe plays a critical role in the development of space weathering features on other airless surfaces (e.g., npFe), its limited availability on Mercury may strongly affect the space weathering features in surface materials. In order to understand how space weathering affects the chemical, microstructural, and optical properties of the surface of Mercury, we can simulate these processes in the laboratory [7]. Here we used pulsed laser irradiation to simulate the short duration, high temperature events associated with micrometeoroid impacts. We used forsteritic olivine, likely present on the Mercurian surface, with varying FeO contents, each mixed with graphite, in our experiments. We then performed reflectance spectroscopy and electron microscopy to investigate the spectral, chemical, and microstructural changes in these samples.

Thompson, Michelle S.↗
DOE OSTI2025

Aerosol Particle Mixing State and Composition at AMF3 (Interim Field Campaign Report)

The campaign is designed to support deployment of aerosol sampling equipment at the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s third ARM Mobile Facility (AMF3) to enable both singe-particle and bulk characterization of the aerosol particles at the field site in Bankhead National Forest, northern Alabama. We are proposing to do this work as part of our proposal “Generalizing aerosol mixing state: synthesis from observations and connection to models,” which has the pre-proposal tracking number PRE-0000035878. The full proposal has Dr. Rachel O’Brien as the Principal Investigator (PI) and Dr. Andy Ault and Dr. Nicole Riemer as Co-PIs. We sought to deploy instruments in winter 2025 and summer 2025 to obtain samples in different seasons, but were delayed by AMF3 set-up and availability of students and PIs. We just completed our first deployment this summer (2025) and we are interested in obtaining samples during this upcoming fall and winter to see the seasonal trends in aerosol mixing state at the site. This will provide a comparison of the impact of biogenic emissions on the mixing state and the chemical composition of the aerosol particles. Overall, the proposed study will provide key information regarding the mixing state of aerosol particles at AMF3 with direct ties to impacts of the particles on cloud formation and light scattering/absorption. From our deployment that ended las week we have some visible observations from our samples. We are observing a regular amount of black carbon on stage 6 of our Micro-Orifice Uniform Deposit Impactor (MOUDI) and we have also observed some short, large increases in aerosol loading. We hope to continue observations of these two features to determine the sources/aging for the black carbon and the physical mixing state as well as the sources for the short (a few minutes) increases in the aerosol loading and determine if the source for these is dust or sea salt or another source. We are also interested in comparing the black carbon we see here to samples collected during the agriculture burns in January/February and in comparing the larger particles to bioaerosols in the spring. To obtain these comparisons, we will need to collect more samples in the other seasons. Finally, we have some size-resolved particle collectors that can be deployed at the same time as the tethered balloon launches. We have discussed with Swarup China about trying to get the timing to work in August and we are interested in coordinating again later, if possible. This will give us ground-level and vertical aerosol mixing state sample sets that will be very exciting to analyze.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1991

Distribution of silicon between kamacite and taenite

Meteorites formed under highly reducing conditions can incorporate substantial amounts of Si in solid solution in their metallic phases. In enstatite meteorites, reduced Si appears in shreibersite, perryite and, in variable amounts, in the kamacite, taenite, and tetrataenite. Microprobe bulk analysis of Si in Fe,Ni particles of aubrites show a large variation from grain to grain; this large compositional range has been attributed to local equilibrium conditions in the specific T and/or fO2 environments in which they are formed. Si concentrations are homogeneous in the kamacite; in contrast, the Ni-rich phases (taenite and tetrataenite) show a characteristic Si profile. Concentrations of this element in tetrataenite are substantially higher than in the adjacent kamacite, and decrease smoothly towards the center of the taenite grain, matching very closely the M-shaped profile of Ni. Other elements with similar distribution patterns are Ge and Cu. A satisfactory explanation for this behavior cannot be given in the absence of experimental data for the diffusion of Si between alpha and gamma-Fe alloys. However, two end-member possibilities can be envisioned: the distribution of Si between kamacite and taenite may be controlled by (1) the crystallographic structure or (2) the chemical composition of the host phases. These possibilities are explored.

Casanova, Ignacio↗
NASA NTRS1991

The chemistry of dense interstellar clouds

The basic theme of this program is the study of molecular complexity and evolution in interstellar and circumstellar clouds incorporating the biogenic elements. Recent results include the identification of a new astronomical carbon-chain molecule, C4Si. This species was detected in the envelope expelled from the evolved star IRC+10216 in observations at the Nobeyama Radio Observatory in Japan. C4Si is the carrier of six unidentified lines which had previously been observed. This detection reveals the existence of a new series of carbon-chain molecules, C sub n Si (n equals 1, 2, 4). Such molecules may well be formed from the reaction of Si(+) with acetylene and acetylene derivatives. Other recent research has concentrated on the chemical composition of the cold, dark interstellar clouds, the nearest dense molecular clouds to the solar system. Such regions have very low kinetic temperatures, on the order of 10 K, and are known to be formation sites for solar-type stars. We have recently identified for the first time in such regions the species of H2S, NO, HCOOH (formic acid). The H2S abundance appears to exceed that predicted by gas-phase models of ion-molecule chemistry, perhaps suggesting the importance of synthesis on grain surfaces. Additional observations in dark clouds have studied the ratio of ortho- to para-thioformaldehyde. Since this ratio is expected to be unaffected by both radiative and ordinary collisional processes in the cloud, it may well reflect the formation conditions for this molecule. The ratio is observed to depart from that expected under conditions of chemical equilibrium at formation, perhaps reflecting efficient interchange between cold dust grains in the gas phase.

Irvine, W. M.↗
NASA NTRS1995

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR reflectivity, Mossbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration (Fe(3+)/Fe(sub tot)) and ranged from approx. 1000 nm (high-Ca pyroxene) to approx. 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the 850 and 1000 nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relatively high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from analyses of soil at the two Viking landing sites.

Morris, Richard V.↗
NASA NTRS1995

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR refectivity, Moessbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to approximately 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration Fe(3+)/Fe(sub tot) and ranged from approximately 1000 nm (high-Ca pyroxene) to approximately 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the approximately 850 and approximately 1000nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relativly high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from the analyses of soil at the two Viking landing sites.

Morris, Richard V.↗
NASA NTRSDate not supplied

Predicting the Seawater Chemistry of an Ocean World Using Machine Learning on Isotopic Measurements of Volatile CO2

Introduction: Given the long time intervals required for data transmission to and from ocean worlds targets, low bandwidth for data transmission, time required for data processing and analysis, and potentially extreme radiation environments (e.g., Europa), it is clear that ocean worlds missions will need more autonomous flight instruments and software in order to achieve established science goals. Protracted time intervals for data analysis (e.g., Europa Lander) strongly motivates the development of rapid, consistent and streamlined methods for interpreting data from flight mass spectrometers to e.g., determine how mass spectra from a plume or surface liquid/ice relates to the surface/subsurface. Since mass spectrometry also has the potential to correctly identify biosignatures[1], it is imperative that such methods for interpreting data are consistent and accurate. We used 848 isotope ratio mass spectra from laboratory analyses of CO2 that interacted with ocean worlds-relevant seawaters as a ‘training’ dataset for ‘unsupervised’ machine learning. In unsupervised learning, characteristics of the data are not labeled or linked, and any similarities found only result from the neural network. CO2 isotopologues analyzed for this dataset mimic the remote measurements of CO2 by a flight mass spectrometer, and are detailed in Theiling [2]. From this dataset, we used measured features of the spectra, such as retention time, intensity, and (isotopologue) mass ratios as inputs for our autoencoder neural network. Our neural network was trained to find similarities in these and other spectral features for seawaters of a particular composition and amount of initial CO2. Successful training then created an output of these similarities for various seawaters, which included MgSO4, Na2SO4, NaCl, MgCl2, KCl, and NaHCO3, and combinations of these salts. We then applied dimensionality reduction techniques such as Principal Component Analysis (PCA), T-Distributed Stochastic Neighbor Embedding (TSNE), and Uniform Manifold Approximation and Projection (UMAP) to demonstrate latent data features as a two-dimensional projection in a unitless, high-dimensional space. In this projection, a data point represents the combined effect of spectral features such as intensity, retention time, and isotope ratio. Our initial UMAP demonstrates data clustering (organization of the data by the neural network) based on the amount of CO2 that had initially interacted with each seawater. Further training using more ‘supervised’ learning techniques demonstrate strong clustering of preliminary data based on initial CO2 concentration, seawater chemical composition, and ionic strength (salinity). Our preliminary work therefore suggests that machine learning has the potential to identify compositional variants of an ocean world seawater based on mass spectra from volatile CO2 measurements. Acknowledgments: This work was funded through a Strategic Task Group at NASA Goddard Space Flight Center. The training dataset was collected through funding from the Oklahoma Space Grant Consortium. References: [1] Pappalardo, R. et al. (2013) Astrobiology, 13, 740–773. [2] Theiling (2020) Icarus, 114216.

Europa↗
DOE OSTI2022

Chemical compatibility of hollow ceramic cenospheres as thermal insulation for high-temperature thermal energy storage applications with molten nitrate salt

An effective insulation material that is both thermally and chemically stable in molten salts could transform the design of molten-salt-based thermal energy storage (TES) tanks. Most current molten salt TES tanks hold the metallic tank structure in direct contact with hot salt inventory, a design which leads to thermal expansion of the tank and triggers stresses that can lead to thermomechanical failures. With an internal insulation to lower the temperature at the tank structure, the extent of thermal expansion can be reduced, thereby reducing expansion-induced stresses and allowing for consideration of lower-cost tank structure materials. Conventional insulation materials are either 1) too porous and allow molten salts to permeate into the matrix, which significantly increases the thermal conductivity or 2) too dense and have a thermal conductivity that cannot provide sufficient thermal insulation. This paper presents an alternative thermal insulation concept using cenospheres which have an alumino-silicate structure. The cost analysis suggests that the low-density cenospheres can be one of the cheapest materials to provide cost-effective thermal insulation. The chemical compatibility of cenospheres is investigated in molten 60 wt% NaNO3/40 wt% KNO3 salt which is close to industrial-grade Solar Salt. This paper shows that diffusion of the sodium and potassium cations from the salt into the cenospheres occurs based on weight analysis, energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The cation diffusion breaks the bridging oxygen bonds and causes volume expansion of the microstructure which is responsible for the failure of the cenosphere particles. The chemical composition of the cenospheres is found to affect their compatibility with molten nitrate salt. A cenosphere product with low iron content showed the best compatibility with an average survival rate of 77.9% +/- 9.8% after 7 days of immersion in the molten nitrate salt. While even the low-iron cenospheres appear to require protection from direct molten salt contact, their slow degradation rate, closed-cell porosity, and low cost hold potential for effective use as internal tank insulation.

14 SOLAR ENERGY↗
DOE OSTI2023

Distinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymers

Synthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push–pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit – alkylthienyl-substituted-benzodithiophene (BDTT) – but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). Here, this methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly – prior to time-consuming device optimization – and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.

14 SOLAR ENERGY↗
NASA NTRS2017

Analyzing the Chemical and Spectral Effects of Pulsed Laser Irradiation to Simulate Space Weathering of a Carbonaceous Chondrite

Space weathering processes alter the chemical composition, microstructure, and spectral characteristics of material on the surfaces of airless bodies. The mechanisms driving space weathering include solar wind irradiation and the melting, vaporization and recondensation effects associated with micrometeorite impacts e.g., [1]. While much work has been done to understand space weathering of lunar and ordinary chondritic materials, the effects of these processes on hydrated carbonaceous chondrites is poorly understood. Analysis of space weathering of carbonaceous materials will be critical for understanding the nature of samples returned by upcoming missions targeting primitive, organic-rich bodies (e.g., OSIRIS-REx and Hayabusa 2). Recent experiments have shown the spectral properties of carbonaceous materials and associated minerals are altered by simulated weathering events e.g., [2-5]. However, the resulting type of alteration i.e., reddening vs. bluing of the reflectance spectrum, is not consistent across all experiments [2-5]. In addition, the microstructural and crystal chemical effects of many of these experiments have not been well characterized, making it difficult to attribute spectral changes to specific mineralogical or chemical changes in the samples. Here we report results of a pulsed laser irradiation experiment on a chip of the Murchison CM2 carbonaceous chondrite to simulate micrometeorite impact processing.

Thompson, M. S.↗