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Low background IR detector and detector array evaluations

A technology program has been underway at Ames since 1978 to develop and evaluate detectors and integrated detector arrays for low-background astronomical applications. The approach is to evaluate existing (less than 24 micron) array technology under low-background conditions, with the aim of adapting and optimizing existing devices. For longer wavelengths, where the technology is much less mature, development is sponsored and devices are evaluated, in both discrete and array formats, for eventual applications. The status of this program has been reported previously. We rely on industrial and university sources for the detectors. Typically, after a brief functionality check in the supplier's laboratory, we work with the device at Ames to characterize its low-background performance. In the case of promising arrays or detectors, we conduct ground-based telescope testing to face the problems associated with real applications. A list of devices tested at Ames is given. In the array category, accumulation-mode charge-injection-devices (AMCIDs) appear repeatedly; this reflects our recent experience with the 2 x 64 and 16 x 16 arrays. Results from the 1 x 16 CID and InSb CCD have been reported. The status of our tests of the discrete Ge:x detectors from Lawrence Berkeley Laboratory are described below. Tests of a 1 x 2 switched sample photoconductor array are just beginning. A 32-channel CMOS multiplexer has been tested at 10 K. Low-temperature silicon MOSFETs and germanium JFETs have also been tested, primarily at Ball Aerospace. This paper describes results to date on three elements of this program: AMCID array, discrete Ge:Ga detectors, and Ge JFET preamplifiers.

Goebel, J. H.↗

Airborne Hyperspectral Imagery for the Detection of Agricultural Crop Stress

Multispectral digital imagery from aircraft or satellite is presently being used to derive basic assessments of crop health for growers and others involved in the agricultural industry. Research indicates that narrow band stress indices derived from hyperspectral imagery should have improved sensitivity to provide more specific information on the type and cause of crop stress, Under funding from the NASA Earth Observation Commercial Applications Program (EOCAP) we are identifying and evaluating scientific and commercial applications of hyperspectral imagery for the remote characterization of agricultural crop stress. During the summer of 1999 a field experiment was conducted with varying nitrogen treatments on a production corn-field in eastern Nebraska. The AVIRIS (Airborne Visible-Infrared Imaging Spectrometer) hyperspectral imager was flown at two critical dates during crop development, at two different altitudes, providing images with approximately 18m pixels and 3m pixels. Simultaneous supporting soil and crop characterization included spectral reflectance measurements above the canopy, biomass characterization, soil sampling, and aerial photography. In this paper we describe the experiment and results, and examine the following three issues relative to the utility of hyperspectral imagery for scientific study and commercial crop stress products: (1) Accuracy of reflectance derived stress indices relative to conventional measures of stress. We compare reflectance-derived indices (both field radiometer and AVIRIS) with applied nitrogen and with leaf level measurement of nitrogen availability and chlorophyll concentrations over the experimental plots (4 replications of 5 different nitrogen levels); (2) Ability of the hyperspectral sensors to detect sub-pixel areas under crop stress. We applied the stress indices to both the 3m and 18m AVIRIS imagery for the entire production corn field using several sub-pixel areas within the field to compare the relative sensitivity of each stress index; and (3) Comparative sensitivity of stress indices to realistic measurement uncertainties. We compare the stress indices calculated with several levels of spectral uncertainty (by shifting the wavelengths) and reflectance uncertainty (by systematically varying the reflectance retrieval code initialization).

Cassady, Philip E.↗

ASK Magazine

Not everyone looks forward to reviews. Dog and pony shows I've heard them called. Exercises in putting together Power Point charts. Other less tasteful descriptions abound, but I won't bother to summarize these. This is a tasteful magazine after all. In this issue, we've assembled a number of articles on the subject of reviews, particularly as they occur in the NASA project world (although we cover the subject from other perspectives too). Veteran NASA Project Manager Marty Davis, in his article Tangled Up in Reviews, writes, "Many people regard reviews as something onerous, but if we can tailor them so that they're not as bad as they have to be, it can be a great benefit to a project manager." Great benefits to the project manager is what you'll find in Marty's story as he describes not only tailoring a single review but the entire lifecycle of reviews in his project. In Jo Gunderson's story, Calling Down the Fire on Yourself, she describes a young NASA Project Manager who does just that because, as he tells her, I needed to know if there was anything that I had overlooked." How he brings fire down on himself at his project review will inspire other young Project Managers, seasoned managers, and anyone else who reads this powerful story. Leave Your Ego at the Door, by Jenny Baer-Reidhart and Ray Morgan, uses reviews to highlight the creative collaboration that existed between NASA and one of its industry partners. The protagonist of this story is a company who took advantage of NASAs expert advice during reviews and accomplished amazing feats as a result. The story also examines how disasters might well have been avoided by two other NASA partners had they been as open-minded as the first company during their reviews. In Roy Malone's story, Standing Offer, a NASA Project Manager describes how he used a crack review team to help him pass a critical certification inspection while he was a Combat Systems Officer in the Navy. Malone invited the reviewers to come back several times so that they would be able to focus in detail on the many areas of the program that would be scrutinized during the certification inspection. These are just a sampling of some of the articles you'll find in this issue of ASK. We believe this issue offers ample evidence that talented Project Managers know how to use reviews to the great benefit of their projects. A talented Project Manager will typically figure out a way to turn any onerous task into a useful learning exercise. These Project Managers demonstrate that the real value of reviews is that they provide a chance to learn something. No dog and pony shows here.

Laufer, Alexander↗

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗

Analysis of Ion-Exchanged ZSM-5, BEA, and SSZ-13 Zeolite Trapping Materials under Realistic Exhaust Conditions

An industry-defined evaluation protocol was used to evaluate the hydrocarbon trapping (HCT) and passive NOx adsorption (PNA) potential for BEA, ZSM-5, and SSZ-13 zeolites with ion-exchanged Pd or Ag. All materials underwent 700 °C degreening prior to exposure to an industry-derived protocol gas stream, which included NOx, ethylene, toluene, and decane as measured trapping species as well as common exhaust gasses CO, H2O, O2, CO2, and H2. Evaluation showed that BEA and ZSM-5 zeolites were effective at trapping hydrocarbons (HCs), as saturation was not achieved after 30 min of exposure. SSZ-13 also stored HCs but was only able to adsorb 20–25% compared to BEA and ZSM-5. The presence of Ag or Pd did not impact the overall HC uptake, particularly in the first three minutes. Pd/zeolites had significantly lower THC release temperature, and it aided in the conversion of the released HCs; Ag only had a moderate effect in both areas. With respect to NOx adsorption, the level of uptake was much lower than HCs on all samples, and Ag or Pd was necessary with Pd being notably more effective. Additionally, only Pd/ZSM-5 and Pd/SSZ-13 continue to store a portion of the NOx above 200 °C, which is critical for downstream selective catalytic NOx reduction (SCR). Hydrothermal aging (800 °C for 50 h) of a subset of the samples were performed: BEA, Pd/BEA, ZSM-5, Pd/ZSM-5, and Pd/SSZ-13. There was a minimal effect on the HC storage, ~10% reduction in capacity with no effect on release temperature; however, only Pd/SSZ-13 showed significant NOx storage after aging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Windshear certification data base for forward-look detection systems

Described is an introduction to a comprehensive database that is to be used for certification testing of airborne forward-look windshear detection systems. The database was developed by NASA Langley Research Center, at the request of the Federal Aviation Administration (FAA), to support the industry initiative to certify and produce forward-looking windshear detection equipment. The database contains high-resolution three-dimensional fields for meteorological variables that may be sensed by forward-looking systems. The database is made up of seven case studies that are generated by the Terminal Area Simulation System, a state-of-the-art numerical system for the realistic modeling of windshear phenomena. The selected cases contained in the certification documentation represent a wide spectrum of windshear events. The database will be used with vendor-developed sensor simulation software and vendor-collected ground-clutter data to demonstrate detection performance in a variety of meteorological conditions using NASA/FAA pre-defined path scenarios for each of the certification cases. A brief outline of the contents and sample plots from the database documentation are included. These plots show fields of hazard factor, or F-factor (Bowles 1990), radar reflectivity, and velocity vectors on a horizontal plane overlayed with the applicable certification paths. For the plot of the F-factor field the region of 0.105 and above signify an area of hazardous, performance decreasing windshear, while negative values indicate regions of performance increasing windshear. The values of F-factor are based on 1-Km averaged segments along horizontal flight paths, assuming an air speed of 150 knots (approx. 75 m/s). The database has been released to vendors participating in the certification process. The database and associated document have been transferred to the FAA for archival storage and distribution.

Switzer, George F.↗

Valorization of mullet roe by‐products for the production of polyunsaturated fatty acids rich oils

Abstract This work examines the potential valorization of mullet roe by‐products for the production of mullet roe oil using mild processes. Three different extraction methods with potential of scale‐up for the food industry, namely pressure (PE), supercritical fluid extraction (SFE), and solvent extraction (SE) are examined. Mild temperature conditions to prevent oil oxidation and (wherever applicable) food‐grade solvents are used. The oil yield, the composition of oils in fatty acids by GC‐FID, the level of oil oxidation (peroxide value (PV), p‐anisidine value (AV), K 232 K 268 , TOTOX)) and the antioxidant activity (DPPH, ABTS) are determined. SE provided the highest oil recovery, followed by SFE and PE (68%, 28% and 10% respectively). The extracted oils had a high concentration of EPA and DHA and a total of 20.7%–24.3% of identified PUFAs among the fatty acids. Oxidation was the lowest in the SFE extracted oil followed by PE, PV was <2.5 meq O2 , AV≤10 and TOTOX <15 in all examined oil samples. Further research is needed to optimize processing conditions for the increase in oil recovery.

Kalogianni, Eleni P.↗

A rapid heating and high magnetic field thermal analysis technique

Abstract A new thermal analysis technique is described that allows measurements to be performed on bulk samples at extreme heating and cooling rates and in high magnetic fields. High heating rates, up to 1000 °C min −1 , are achieved through electromagnetic induction heating of a custom-built apparatus fitted with commercial thermal analysis heads and sensor. Rapid cooling rates, up to 100 °C min −1 , are enabled by gas quenching and the small thermal mass of the induction furnace. The custom apparatus is designed to fit inside a superconducting magnet capable of fields up to 9 Tesla. This study demonstrates that the instrument is capable of collecting accurate thermal analysis data in high magnetic fields and rapidly acquiring data for dynamic processes. While the full potential of the technique is still unrealized, currently, it can provide insight into phenomena at time scales relevant to heat treatment in many industrial processes and into little understood effects of high magnetic field processing.

47 OTHER INSTRUMENTATION↗

Optimization of direct aging temperature of Ti free grade 300 maraging steel manufactured using laser powder bed fusion (LPBF)

Maraging steels are of interest to the tool and die industry owing to their high strength, toughness and machinability. Additive manufacturing technologies like laser powder bed fusion (LPBF) can result in a paradigm shift in the design of maraging steel tools. Here, the lack of precipitates, in combination with solute segregation and non-equilibrium microstructure in Grade 300 maraging steel fabricated via LPBF makes the steel amenable to strengthening via direct aging post fabrication instead of the conventional solution treatment and aging. In this study we have focused on optimizing the direct aging temperature for a Ti-free Grade 300 maraging steel fabricated via LPBF for two different aging times. Through strain hardening analysis and detailed microstructural characterization, we show that direct aging at a temperature of 440 °C for 6 h resulted in the best strength-ductility combination. Aging samples at a lower temperature or shorter time resulted in no strain hardening prior to necking as a result of lower fraction of reverted austenite, whereas aging samples at a higher temperature resulted in extensive recrystallization of martensite, coarsening of precipitates, and extensive austenite reversion, resulting in softening of the fabricated parts.

36 MATERIALS SCIENCE↗

X-Ray Computed Tomography Inspection of the Stardust Heat Shield

The "Stardust" heat shield, composed of a PICA (Phenolic Impregnated Carbon Ablator) Thermal Protection System (TPS), bonded to a composite aeroshell, contains important features which chronicle its time in space as well as re-entry. To guide the further study of the Stardust heat shield, NASA reviewed a number of techniques for inspection of the article. The goals of the inspection were: 1) to establish the material characteristics of the shield and shield components, 2) record the dimensions of shield components and assembly as compared with the pre-flight condition, 3) provide flight infonnation for validation and verification of the FIAT ablation code and PICA material property model and 4) through the evaluation of the shield material provide input to future missions which employ similar materials. Industrial X-Ray Computed Tomography (CT) is a 3D inspection technology which can provide infonnation on material integrity, material properties (density) and dimensional measurements of the heat shield components. Computed tomographic volumetric inspections can generate a dimensionally correct, quantitatively accurate volume of the shield assembly. Because of the capabilities offered by X-ray CT, NASA chose to use this method to evaluate the Stardust heat shield. Personnel at NASA Johnson Space Center (JSC) and Lawrence Livermore National Labs (LLNL) recently performed a full scan of the Stardust heat shield using a newly installed X-ray CT system at JSC. This paper briefly discusses the technology used and then presents the following results: 1. CT scans derived dimensions and their comparisons with as-built dimensions anchored with data obtained from samples cut from the heat shield; 2. Measured density variation, char layer thickness, recession and bond line (the adhesive layer between the PICA and the aeroshell) integrity; 3. FIAT predicted recession, density and char layer profiles as well as bondline temperatures Finally suggestions are made as to future uses of this technology as a tool for non-destructively inspecting and verifying both pre and post flight heat shields.

McNamara, Karen M.↗

Deriving Earth Science Data Analytics Requirements

Data Analytics applications have made successful strides in the business world where co-analyzing extremely large sets of independent variables have proven profitable. Today, most data analytics tools and techniques, sometimes applicable to Earth science, have targeted the business industry. In fact, the literature is nearly absent of discussion about Earth science data analytics. Earth science data analytics (ESDA) is the process of examining large amounts of data from a variety of sources to uncover hidden patterns, unknown correlations, and other useful information. ESDA is most often applied to data preparation, data reduction, and data analysis. Co-analysis of increasing number and volume of Earth science data has become more prevalent ushered by the plethora of Earth science data sources generated by US programs, international programs, field experiments, ground stations, and citizen scientists.Through work associated with the Earth Science Information Partners (ESIP) Federation, ESDA types have been defined in terms of data analytics end goals. Goals of which are very different than those in business, requiring different tools and techniques. A sampling of use cases have been collected and analyzed in terms of data analytics end goal types, volume, specialized processing, and other attributes. The goal of collecting these use cases is to be able to better understand and specify requirements for data analytics tools and techniques yet to be implemented. This presentation will describe the attributes and preliminary findings of ESDA use cases, as well as provide early analysis of data analytics toolstechniques requirements that would support specific ESDA type goals. Representative existing data analytics toolstechniques relevant to ESDA will also be addressed.

data analytics↗

Variation of lead isotopic composition and atomic weight in terrestrial materials (IUPAC Technical Report)

The isotopic composition and atomic weight of lead are variable in terrestrial materials because its three heaviest stable isotopes are stable end-products of the radioactive decay of uranium ( 238 U to 206 Pb; 235 U to 207 Pb) and thorium ( 232 Th to 208 Pb). The lightest stable isotope, 204 Pb, is primordial. These variations in isotope ratios and atomic weights provide useful information in many areas of science, including geochronology, archaeology, environmental studies, and forensic science. While elemental lead can serve as an abundant and homogeneous isotopic reference, deviations from the isotope ratios in other lead occurrences limit the accuracy with which a standard atomic weight can be given for lead. In a comprehensive review of several hundred publications and analyses of more than 8000 samples, published isotope data indicate that the lowest reported lead atomic weight of a normal terrestrial materials is 206.1462 ± 0.0028 (k = 2), determined for a growth of the phosphate mineral monazite around a garnet relic from an Archean high-grade metamorphic terrain in north-western Scotland, which contains mostly 206 Pb and almost no 204 Pb. The highest published lead atomic weight is 207.9351 ± 0.0005 (k = 2) for monazite from a micro-inclusion in a garnet relic, also from a high-grade metamorphic terrain in north-western Scotland, which contains almost pure radiogenic 208 Pb. When expressed as an interval, the lead atomic weight is [206.14, 207.94]. It is proposed that a value of 207.2 be adopted for the single lead atomic-weight value for education, commerce, and industry, corresponding to previously published conventional atomic-weight values.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Influence of Thermophysical Property Variability on Thermal Predictions of Ti-6Al-4V

The additive manufacturing (AM) industry has experienced rapid growth in recent decades as industrial interest in the process has grown. Because of this, there are many groups interested in simulations of the AM process. However, the influence of thermophysical property variability on the melt pool geometry during processing of various AM alloys is unclear. The goal of my work at NASA Langley Research Center (LaRC) was to characterize this influence on Ti-6Al-4V during AM processing alongside developing a tool to enable equivalent studies on other AM materials. To facilitate this process, a database tool was developed to contain and organize thermophysical data previously reported by primary sources. The specific thermophysical properties of interest for this study were density, specific heat capacity, and conductivity. Thermal diffusivity was calculated using the other three properties. This data was then fit with a Gaussian distribution and then randomly sampled from using Monte Carlo random value sampling. Using the Rosenthal equation, this sample data was used to simulate the temperature field during additive manufacturing and extract the melt pool geometry. Specifically, the melt pool’s length, width, and depth. This process was repeated an arbitrary number of times, with the default being 1000. Once this information was obtained, histograms were made showing the distributions of the sizes of the melt pool’s length, width, and depth. Representative statistical metrics of the distributions were calculated (mean, standard deviation, and coefficient of variance). This work found that at the simulated processing values, the melt pool’s width and depth had a 5.7% variation while the length had a 3.2% variation. Additionally, a tool was constructed to graph a thermal color map representation of the melt pool for specific, arbitrary values of density, specific heat, and conductivity. This tool allowed for more efficient plotting of individual queries of the thermophysical properties. The results that were observed in the research were that values reported in literature vary and this variance can have a significant impact on the simulation. Predictions of the melt pool’s dimensions show that length has a standard deviation of approximately 6 μm, width has a standard deviation of approximately 5 μm, and depth can vary by approximately 3 μm. Considering the mean sizes of length, width, and depth are 185 μm, 88 μm, and 44 μm respectively, such a deviation is significant. This shows that depth, for example, could be more than 10% larger or smaller than expected. This demonstrates that variability in the reported thermophysical properties are not negligible and should be expected to have an influence on the results of the laser powder bed fusion additive manufacturing process. When simulating this process in the future, measures should be taken to account for this discrepancy and the uncertainty involved

Justin Martin↗

Oil price states and drivers: An analysis of the second-month spot-futures price differential

Oil remains a dominant component of global energy use, and its price, characterized by frequent changes and an ever-present potential for large swings, continues to be a focus of industry participants, policymakers and analysts attention. Here, this study examines the behavior of future spot oil prices using a continuous-time hidden Markov model (HMM) and daily price data spanning years 2007 to 2024. We identify six states in the second-month WTI spot-futures price differential and assess the roles of eleven futures price, quantity, financial market, and geopolitical/volatility variables in each state. The model yields several insights into the workings of the oil market and the relative roles of these drivers. We find support for several theoretical and empirical findings in the oil market literature, including the role of inventory, volatility/risk, and market responses to contango/backwardation in futures markets. A novel finding is that “normal contango” conditions represent a significant portion of next-day states in our in-sample data. Under the most volatile normal contango state, many of the oil market drivers differ markedly in coefficient signs and magnitudes from those in other states. The resulting model also performed well out-of-sample and would, in addition to understanding the impact of market drivers, be useful for short-term forecasting. Overall, the findings highlight the highly non-linear, regime-dependent interactions of the oil price and its drivers, emphasizing the importance of detailed information to market stakeholders.

Oladosu, Gbadebo A. [Oak Ridge National Laboratory↗

Evaluating the Transport Mechanism for Lignocellulosic Inhibitors in Zymomonas mobilis

The conversion of lignocellulosic biomass to biofuels and bioproducts is limited by small inhibitory molecules generated during the pretreatment process. The diverse compounds within the cell wall hydrolysate including aldehydes, carboxylic acids, phenolics, and alcohols inhibit microbial growth by disrupting microbial membranes. Although Zymomonas mobilis combines high ethanol productivity with hopanoid-rich membranes that confer solvent tolerance, hydrolysate compounds still inhibit microbial growth. One proposed mitigation strategy is to pump these molecules out through active transport processes, reducing direct toxicity. However, if passive permeation rates are high, active transport would create a futile cycle where the exported molecules diffuse back in, creating a net drag on fitness. To investigate this hypothesis, we measure the passive permeation for thirty-three lignocellulose derived compounds using atomistic molecular dynamics simulations with enhanced sampling. Permeability coefficients determined spanned more than eight orders of magnitude driven largely by the balance between hydrophobicity and polarity. Hydrophobic inhibitors such as aromatic acids, aldehydes, and short chain alcohols readily partitioned into the membrane and showed high permeability consistent with rapid passive influx and strong toxicity. Most polar molecules have lower but still appreciable permeation rates, with only the most polar sugars having low permeabilities. By integrating these predictions together with hydrolysate composition information, we find that most of these molecules are so permeable that futile cycles where passive permeation overwhelms efflux is highly likely. These findings provide a predictive framework for strain engineering, highlighting that, for highly permeable inhibitors, reducing extracellular inhibitor concentrations through hydrolysate detoxification, pretreatment optimization, or dilution may be necessary to mitigate futile cycling and improve microbial productivity in industrial biorefineries.

Zymomonas mobilis↗

Addressing Critical Problems in Materials Science Through Multiscale and Multimode Characterization (Project 1); Characterization and Optimization of Novel Triple-Conducting Oxide Materials for Energy Applications (Project 2) (CRADA Final Report)

PROJECT 1: Address critical problems in materials science and simultaneously advance the state-of-the-art in multiscale and multimode characterization using the combined advanced analytical capabilities and expertise of Colorado School of Mines (CSM) and the National Renewable Energy Laboratory (NREL). The primary effort of the Phase I of this CRADA is to establish the International Center for Multiscale Characterization using shared resources at both NREL and CSM. Phase II will focus on capability development and marketing, choosing candidate materials science issues in the areas of structure imaging, chemical composition mapping, and correlating properties and performance of materials for impact in energy-related, environmental and critical materials areas. The CRADA will be modified to include specific topics of concern in materials science to industry member partners. Advanced analytical capabilities and expertise at CSM and NREL will be used to advance materials understanding and performance through characterization of multiscale phenomena including structural imaging, chemical composition mapping, and other techniques correlating properties and performance of materials. PROJECT 2: As part of the International Center for Materials Characterization, work under Modification #1 will be led by Colorado School of Mines (CSM), working in collaboration with NREL staff to mentor and advise CSM postdoctoral researchers on set up of diffusion annealing experiments. The purpose of the modification is to provide for NREL staff to mentor and advise CSM postdoctoral researchers on set up of diffusion annealing experiments, including mentoring and advising the CSM-NREL team on proper Secondary Ion Mass Spectrometry (SIMS) data analysis as needed. SIMS measurements of 10-20 samples will be performed at NREL during the project duration.

08 HYDROGEN↗

Industrial Scalable Additives for Enhanced Decomposition of Plastic Waste Through Photocatalysis

Polymer pollution is a dangerous environmental problem that can lead to the spread of toxic chemicals and microplastics throughout aquatic biomes. Commonly littered plastic from consumer goods and products with a limited or single use can be embedded with photocatalysts to avoid an increase in the amount of plastic present in Earth’s bodies of water. In this work, the photocatalyst nanoparticles, less than 100 nm particle size, were integrated into polyethylene terephthalate, high-density polyethylene, low-density polyethylene, and polystyrene and exposed under ultraviolet light over two independent experimental trials examining both the environmental factors impacting decay and the physical parameters required to implement this solution on a large scale. The plastics were chosen due to their prolific use in items such as grocery bags, bottles, and packaging. The first half of the project examined the effects of water and light frequency on polymer decay, and the second half of the project examined photodecomposition of polymer films. We report that low-density and high-density polyethylene films with titanium dioxide decayed approximately 11.7 and 9.6 faster than control samples, respectively. With an estimated price of less than half the cost of a shopping bag for titanium catalyst integration and a retention of the polymer’s tensile strength with a 2 wt% catalyst concentration, photocatalytic decomposition is a feasible, scalable method for the prevention and future reduction of polymer waste from realistic products littered in the environment.

36 MATERIALS SCIENCE↗

Regional Feedstock Partnership Biomass Quality Assessment Final Report

The United States (U.S.) Department of Energy (DOE) developed the Billion-Ton Vision to enable production of one-billion tons of sustainable, reliable biomass for the bioenergy industry by 2030 (Perlack et al., 2005). The Sun Grant Regional Feedstock Partnership (RFP) was organized to fill information gaps and validate biomass yield assumptions related to the Billion-Ton Study (Owens, 2018; Owens, Karlen, and Lacey, 2016). Along with the more than 130 scientific publications generated from these studies, yield and sustainability data from the RFP field trials not only validated the Billion-Ton estimates, but were critical in developing both the U.S. Billion-Ton Update report in 2011 and the 2016 Billion-Ton Report (DOE, 2011; 2016). The intention of this biomass quality assessment report is to build on these initial successes from the RFP field trials by focusing on variability in biomass quality data necessary to evaluate conversion performance. This report contains a summary of chemical quality results from samples collected as part of the RFP field trials. This report focuses on assessment of the impact of experimental agronomic designs on biomass properties followed by analyses of the impact of environmental and production variables on biomass properties. Datasets include species and other genetic variables, fertilizer treatments, harvest information, and yield, as well as other publicly available data such as precipitation, temperature, soil properties, and drought. The key outcomes from this chemical quality focused assessment have included: • Complete evaluation of the impacts of agronomic designs, genetics, and environmental conditions on chemical properties for Miscanthus, switchgrass, sorghum, energycane, mixed perennial grasses, and shrub willow short-rotation feedstocks • Over 30 peer review publications and technical reports focused on variability in quality data • Development of spatial and temporal environmental quality prediction maps for Miscanthus and switchgrass feedstocks allowing for comprehensive evaluation of variability in feedstock chemical quality across U.S. regions and over multiple harvest years

09 BIOMASS FUELS↗