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At least 559 records · Page 31

Block copolymer self-assembly derived mesoporous magnetic materials with three-dimensionally (3D) co-continuous gyroid nanostructure

Magnetic nanomaterials are gaining interest for their many applications in technological areas from information science and computing to next-generation quantum energy materials. While magnetic materials have historically been nanostructured through techniques such as lithography and molecular beam epitaxy, there has recently been growing interest in using soft matter self-assembly. In this work, a triblock terpolymer, poly(isoprene-block-styrene-block-ethylene oxide) (ISO), is used as a structure directing agent for aluminosilicate sol nanoparticles and magnetic material precursors to generate organic–inorganic bulk hybrid films with co-continuous morphology. After thermal processing into mesoporous materials, results from a combination of small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are consistent with the double gyroid morphology. Nitrogen sorption measurements reveal a type IV isotherm with H1 hysteresis, and yield a specific surface area of around 200 m 2 g −1 and an average pore size of 23 nm. The magnetization of the mesostructured material as a function of applied field shows magnetic hysteresis and coercivity at 300 K and 10 K. Comparison of magnetic measurements between the mesoporous gyroid and an unstructured bulk magnetic material, derived from the identical inorganic precursors, reveals the structured material exhibits a coercivity of 250 Oe, opposed to 148 Oe for the unstructured at 10 K, and presence of remnant magnetic moment not conventionally found in bulk hematite; both of these properties are attributed to the mesostructure. This scalable route to mesoporous magnetic materials with co-continuous morphologies from block copolymer self-assembly may provide a pathway to advanced magnetic nanomaterials with a range of potential applications.

Chemistry↗

Space Launch System and Missions to Near Rectilinear Halo Orbits

The first major evolution of NASA’s Space Launch System (SLS) will begin its flights starting in the mid-2020’s. This new configuration, called Block 1B, replaces the Interim Cryogenic Propulsion Stage with a larger Exploration Upper Stage (EUS). The additional capability provided by the new upper stage will allow SLS to send heavier payloads into deep space. One destination of interest to the SLS program is called a Near Rectilinear Halo Orbit (NRHO). This is a type of lunar orbit with multiple advantages for deep space exploration. These benefits include Earth/lunar access, low station-keeping requirements, and high communication potential with Earth. Therefore, it is a leading candidate for the proposed Lunar Orbital Platform-Gateway (LOP-G). This paper will provide a detailed assessment of the SLS Block 1B requirements and capabilities for sending payloads to an NRHO. Analysts at Marshall Space Flight Center are producing a multi-year mission availability scan for the SLS Block 1B configuration to a predefined NRHO orbit. The analysis produces an optimized trajectory for each day of the scan window. A maximized payload and minimized propellant requirement are determined for each day. All maneuvers from launch to the end of the Trans-Lunar-Injection (TLI) are being modeled as finite burns. Injections into an NRHO are being modeled as impulsive maneuvers. The payload element is arbitrary, but includes sufficient mass to represent a large habitat or propulsion module. The resulting parameters of payload capability, delta-v requirements, and launch windows length vary over the course of the scan. Many launch days in the scan are eliminated in post-processing as they violate mission constraints such as payload mass and propellant usage to insert into an NRHO. Based off previous one-year scan results for the SLS Block 1B Design Analysis Cycle 2 (DAC-2), it is expected that there will be one to three days per week where the payload is able to insert into an NRHO within SLS constraints objectives. This scan provides results for longer than one-year, allowing analysts to better understand the launch availability and energy requirements of SLS Block 1B over time. The in-space mission design and scans utilize Copernicus, an n-body trajectory optimization tool originally developed out of the University of Texas at Austin with further development at Johnson Space Center in Houston, TX. To seed the in-space trajectory, Copernicus uses a plugin to call a database of SLS ascent trajectories optimized in the Program to Simulate Optimized Trajectories II (POST2). The ascent trajectories are developed using a framework that parametrizes payload mass and LEO inclination, and targets a 100 nmi (nautical mile) altitude circular parking orbit. Though this analysis is specific to the SLS program, it will provide a summary of mission design benefits and constraints associated with generic NRHO access, and may be applied to other programs or concepts that will utilize this orbit.

Statham, T. L.↗

Microstructural, Corrosion and Mechanical Characterization of Friction-Stir Welded Joints Between Aluminum and Magnesium Alloys

Friction Stir Welding (FSW) of Aluminum-Magnesium (Al-Mg) alloys has garnered increasing attention due to its wide-ranging applications in the automotive and aerospace industries. The microstructural, corrosion, and mechanical properties of FSW Al-Mg welds under selected conditions are critical factors that must be well-investigated to ensure their durability and performance. In this study, electrochemical tests, including Open Circuit Potential (OCP), Linear Polarization Resistance (LPR), Potentiodynamic Polarization Scan (PD), and Electrochemical Impedance Spectroscopy (EIS), have been used to analyze the corrosion resistance of these welds, along with weight loss measurements through cyclic corrosion testing (CCT) and surface evolution via SEM over an 8-week period. Mechanical properties are evaluated through microindentation, nanoindentation, fatigue, and lap-shear tests. The results of the electrochemical tests reveal that the corrosion properties of the center weld zone differ from those of the two base alloys. Indentation tests indicate that the weld zone behaves differently from the base alloys. Surprisingly, the lap shear strength did not decrease significantly even after 8 weeks of cyclic corrosion testing, indicating that the joint prevented any ingress of the electrolyte. Fatigue testing showed that applying an adhesive between the Al and Mg joint improved the fatigue life to some extent, although the corrosion resistance reduced due to the discontinuous bonding of the adhesive layer. Overall, these findings highlight the importance of investigating the corrosion and mechanical properties of FSW Al-Mg welds and provide valuable insights for future modeling works.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Dosimetric delivery validation of dynamically collimated pencil beam scanning proton therapy

Pencil beam scanning (PBS) proton therapy target dose conformity can be improved with energy layer-specific collimation. One such collimator is the dynamic collimation system (DCS), which consists of four nickel trimmer blades that intercept the scanning beam as it approaches the lateral extent of the target. While the dosimetric benefits of the DCS have been demonstrated through computational treatment planning studies, there has yet to be experimental verification of these benefits for composite multi-energy layer fields. The objective of this work is to dosimetrically characterize and experimentally validate the delivery of dynamically collimated proton therapy with the DCS equipped to a clinical PBS system. Approach. Optimized single field, uniform dose treatment plans for 3 × 3 × 3 cm 3 target volumes were generated using Monte Carlo dose calculations with depths ranging from 5 to 15 cm, trimmer-to-surface distances ranging from 5 to 18.15 cm, with and without a 4 cm thick polyethylene range shifter. Treatment plans were then delivered to a water phantom using a prototype DCS and an IBA dedicated nozzle system and measured with a Zebra multilayer ionization chamber, a MatriXX PT ionization chamber array, and Gafchromic™ EBT3 film. Main results. For measurements made within the SOBPs, average 2D gamma pass rates exceeded 98.5% for the MatriXX PT and 96.5% for film at the 2%/2 mm criterion across all measured uncollimated and collimated plans, respectively. For verification of the penumbra width reduction with collimation, film agreed with Monte Carlo with differences within 0.3 mm on average compared to 0.9 mm for the MatriXX PT. Significance. We have experimentally verified the delivery of DCS-collimated fields using a clinical PBS system and commonly available dosimeters and have also identified potential weaknesses for dosimeters subject to steep dose gradients.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Smaller and faster: a review of conventional and nanocalorimetry techniques for determining thermophysical properties of nuclear materials

Thermal analysis of nuclear materials is critical for the advancement of nuclear technology. The heat effects associated with heat capacity, phase transformation, and radiation damage can be measured with conventional calorimeters. However, conventional calorimetric techniques are often restricted in terms of heating rate and sample mass, especially when studying the limited amounts of materials subject to extreme conditions. In this review, we summarize conventional calorimetric studies of critical thermophysical and thermochemical properties of pure actinide metals (U, Np, Am, Pu), fast reactor metallic fuel alloy systems (U–Zr, U–Pu–Zr, Pu–U, Pu–Zr), and actinide oxides that are primary constituents or transmutation products in light water reactor fuel rods (U–O, Np–O, Am–O, Pu–O, Pu–U–O). Adiabatic and drop calorimetry have been the primary techniques used for these studies, however the development of fast scanning calorimetry using micro-electro-mechanical-based systems allows determination of thermodynamic properties from smaller sample masses. We report recent investigations that leverage the fast heating rates of nanocalorimetry by itself or combined with other characterization techniques. Furthermore, we then discuss opportunities for nanocalorimetry to provide solutions to some of the technical challenges inherent in thermal analysis of nuclear materials, namely a reduction in sample activity, emulating heating transients, investigation of phase evolution in irradiated samples, and characterization of radiation damage evolution. Nanocalorimetry has the potential to significantly advance the understanding of thermophysical properties in nuclear materials and thus accelerate the development of nuclear technology.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Heat Transfer and Thermal Stability Research for Advanced Hydrocarbon Fuel Technologies

In recent years there has been increased interest in the development of a new generation of high performance boost rocket engines. These efforts, which will represent a substantial advancement in boost engine technology over that developed for the Space Shuttle Main Engines in the early 1970s, are being pursued both at NASA and the United States Air Force. NASA, under its Space Launch Initiative s Next Generation Launch Technology Program, is investigating the feasibility of developing a highly reliable, long-life, liquid oxygen/kerosene (RP-1) rocket engine for launch vehicles. One of the top technical risks to any engine program employing hydrocarbon fuels is the potential for fuel thermal stability and material compatibility problems to occur under the high-pressure, high-temperature conditions required for regenerative fuel cooling of the engine combustion chamber and nozzle. Decreased heat transfer due to carbon deposits forming on wetted fuel components, corrosion of materials common in engine construction (copper based alloys), and corrosion induced pressure drop increases have all been observed in laboratory tests simulating rocket engine cooling channels. To mitigate these risks, the knowledge of how these fuels behave in high temperature environments must be obtained. Currently, due to the complexity of the physical and chemical process occurring, the only way to accomplish this is empirically. Heated tube testing is a well-established method of experimentally determining the thermal stability and heat transfer characteristics of hydrocarbon fuels. The popularity of this method stems from the low cost incurred in testing when compared to hot fire engine tests, the ability to have greater control over experimental conditions, and the accessibility of the test section, facilitating easy instrumentation. These benefits make heated tube testing the best alternative to hot fire engine testing for thermal stability and heat transfer research. This investigation used the Heated Tube Facility at the NASA Glenn Research Center to perform a thermal stability and heat transfer characterization of RP-1 in an environment simulating that of a high chamber pressure, regenerative cooled rocket engine. The first step in the research was to investigate the carbon deposition process of previous heated tube experiments by performing scanning electron microscopic analysis in conjunction with energy dispersive spectroscopy on the tube sections. This analysis gave insight into the carbon deposition process and the effect that test conditions played in the formation of deleterious coke. Furthermore, several different formations were observed and noted. One other crucial finding of this investigation was that in sulfur containing hydrocarbon fuels, the interaction of the sulfur components with copper based wall materials presented a significant corrosion problem. This problem in many cases was more life limiting than those posed by the carbon deposition process. The results of this microscopic analysis was detailed and presented at the December 2003 JANNAF Air-Breathing Propulsion Meeting as a Materials Compatibility and Thermal Stability Analysis of common Hydrocarbon Fuels (reference 1).

DeWitt, Kenneth↗

Unveiling Structural Heterogeneity and Imbalance of Gold Decahedral Nanoparticles using Four-dimensional Scanning Transmission Electron Microscopy

Multi-twinned structures have been observed in technologically important crystal systems, for example diamond cubic and face-centered cubic (FCC) lattices, that include materials such as diamond, silicon, a wide range of noble metals, and their nanoscale counterparts. Beyond atomic building blocks, the special arrangements also occur in the self-assembly of nanoparticles (NP) and μm-sized colloidal particles and occupy parts of their phase diagrams. Spanning a wide range of length scales, the universality of the structures arises when the systems attempt to achieve multitwinned structures by overcoming geometric misfits during minimizing surface energies with entirely {111} or close-packing facets. While it is fundamental to understand how strain is sustained upon twinned structures and symmetry breaking, the knowledge will be paramount in practical aspects such as guiding and controlling the thin film growth, anisotropic NP growth, and self-assembly of NPs. Au decahedral (Dh) NP, as the most prevalent multi-twinned model system, fits five tetrahedral motifs into a circle by sharing an axis resulting in a geometric misfit angle of 7.35°, or a disclination with power of -7.35°. Postulating how Au FCC lattice adopts the misfit, theoretical models have been developed to address the underlying lattice symmetry and inhomogeneous strain distribution separately. Yet, experimental reports regarding the former have been limited due to the relatively large X-ray beam sizes that do not fit the sizes of NPs. On the other hand, though the latter has been widely adapted in the thermodynamics of small (<10 nm) multi-twinned nanoparticles, previous literature has shown that, at edge length of 17 nm, the theory’s is invalidated by shear strain that is observed in a defect-free Au Dh NP by high-resolution transmission electron microscopy (HR-TEM) imaging. Though the advancement of aberrationcorrected scanning transmission electron microscopy (AC-STEM) imaging and ab initio calculation techniques brings new opportunities, along with challenges in complicated image analysis and limitation in particle size (usually below 10 nm), the gap between nanoscale and mesoscale has never been extended to gain insight from atomic system with straightforward interaction potentials.

4D-STEM↗

Engineered Barrier System R&D and International Collaborations – LANL (FY20): Spent Fuel and Waste Disposition

The United States Department of Energy’s Spent Fuel and Waste Disposition (SFWD) program is investigating the design and safety function of generic nuclear geologic repositories in a variety of geologic settings (salt, argillite, and crystalline rock). Different configurations and loadings of spent nuclear fuel and waste within disposal canisters are also being investigated, some of which have the potential to generate repository temperatures higher than previously considered (i.e., temperatures >100ºC) by foreign and domestic concepts. This report expands on engineered barrier material stability in a high temperature crystalline rock repository through high temperature hydrothermal experiments. Experiments were designed to develop engineered barrier system (EBS) concepts in a hightemperature crystalline environment in 1) bentonite-Grimsel Granodiorite interactions, 2) bentonite-cement reactions, and 3) interaction between waste canister materials and bentonite. Experiment results are applied to understanding long-term repository performance in terms of radionuclide isolation. One hydrothermal experiment was completed in the rocking autoclaves at LANL in FY-20: IEBS-6 (Grimsel Granodiorite + Wyoming bentonite + cured ordinary Portland cement + Grimsel Granodiorite synthetic groundwater, 250ºC/150 bar, 8 weeks). Several other experiments were planned but were delayed due to the COVID-19 pause in laboratory work. In addition, some characterization of the reaction products of experiments conducted in FY-20 was prevented by COVID-19. Mineral phase chemistry was not measured via electron microprobe analyses for IEBS-6. Quantitative X-ray diffraction results from IEBS-6 and HBT-1 were not completed. The missing analyses and discussion of the results will be included in next year’s report. New characterization that was completed includes scanning electron microscopy of reaction products from IEBS-6, quantitative X-ray diffraction results are presented from IEBS-1 through IBES-5, preliminary scanning electron microscope images and chemical analyses for IEBS-6, X-ray diffraction of the clay fraction from all experiments, measurement/imaging of mineral growth on the surface of steel coupons. Major observations pertaining to bentonite stability in a Grimsel Granodiorite environment include the stability of Na-montmorillonite at 250°C, the formation of trace CSH phases, and the formation of bentonite colloids on experiment cooling. The addition of a cured chip of Portland cement to the bentonite-Grimsel system results in slightly higher pH values and the formation of diverse secondary mineral phases that were not observed in the previous experiments (e.g., analcime, garronite, CSH phases). The new characterization efforts related to the interaction of stainless-steel coupons and bentonite clay focused on thickness and mineralogy of phases that formed at the steel surface. In Wyoming bentonite + Grimsel Granodiorite systems, newly formed minerals at the bentonitesteel coupon interface included alteration of the outermost steel edge to Fe,Cr-oxide phases, followed by Fe-rich phyllosilicates (Fe-saponite, chlorite) and interbedded Fe,Cr,Ni-sulfide phases (pentlandite). Hydrothermal experiments were completed to assess uranium-carbonate complexation at conditions relevant to high-temperature disposal. Autoclave solubility experiments were conducted at 150 to 250ºC with a range of carbonate and uranium concentrations. The experiment results were characterized via situ UV-Visible spectroscopy and synchrotron-based in situ XAS techniques. Results show a significant decrease in the stability of uranyl-carbonate complexes at temperatures above 100ºC along with the precipitation of uranium oxides. Further, at T > 200ºC, results show that uranyl-hydroxyl complexes control solubility of uranium instead of the previously predicted uranyl-carbonate species. These results are significant for understanding the mobility of uranium in the EBS, which will likely contain carbonate-rich fluids. International research efforts focused on three main areas: 1) participation in international conferences, 2) building collaborations with foreign repository programs, and 3) the initiation of an experimental program to complement the full-scale HotBENT test at the Grimsel test site. This experiment included Wyoming bentonite + low carbon steel + Grimsel Granodiorite synthetic groundwater and was run at the planned maximum temperature of the HotBENT test (200°C). Complete characterization of reaction products was hindered by disruptions to laboratory work but will be reported in the next FY. The experimental results obtained in FY-20 continue to document the wide-ranging effects of bulk composition and pressure-temperature conditions in the mineralogical and geochemical evolution of a high-temperature repository environment. Concepts developed will be used to inform models of long-term material stability in a generic crystalline rock-hosted repository.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DISTRIBUTION OF ION-EXCHANGEABLE RARE EARTH ELEMENTS AND CRITICAL MINERALS IN COAL-HOSTED CLAYS OF THE POWDER RIVER BASIN, WY

Increasing demand for a more robust domestic supply of rare earth elements (REE) and critical minerals (CM) has led to significant investigation into unconventional sources. Coal and coal byproducts from the Powder River Basin (PRB) of Wyoming are potential sources of REE but lack complete characterization of mineral hosts including ion-adsorption clays (IACs). IACs, which provide a substantial portion of the global REE supply, form when hydrated REE complexes are physiosorbed to negatively charged sites on clay surfaces. Typical IAC minerals include kaolinite, illite, and smectite. REE complexes are easily leached from IACs via ion exchange, making them economically attractive. However, research regarding the partitioning behaviors of strategic metals into PRB coal-hosted clays is limited. This project aims to quantify the modes of occurrence and distribution of REE and CM in clay minerals derived from PRB coals. Strategic metals investigated in this project have historic production or promising deposits within the PRB and/or high anticipated supply risk, and include: REE (lanthanides and Y), V, Ti, platinum group elements (PGE; Pt, Pd, Rh, Ru, Ir, Os), Al, Co, Ga, Zr, and W. Semi-quantitative compositional data from portable x-ray fluorescence spectroscopy (pXRF) on coal core from the PRB is consistent with the known correlation between REE and Al content, suggesting increased REE abundance will be found in clay-rich units. pXRF data also identifies elevated V, Ti, Co, and Zr correlated with Al. Preliminary x-ray diffraction (XRD) data indicates kaolinite, illite, and dickite are abundant minerals in overburden and clay-rich partings. Quantitative analysis via inductively coupled plasma mass spectrometry (ICP-MS) provides insights into REE and CM fractionation in coals as we compare trace metal occurrence to variations in mineralogy. Additionally, we apply scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) data to correlate clay size and morphology to trace metal occurrence. Our findings supplement a broader effort to couple REE and CM extraction with existing domestic coal production and contribute to the fundamental understanding of adsorption processes that occur in low-temperature basin environments.

Stuart, Sophia↗

Synthesis and Characterization of Silver-Modified Nanoporous Silica Materials for Enhanced Iodine Removal

In aquatic environments, the presence of iodine species, including radioactive isotopes like 129 I and I 2 , poses significant environmental and health concerns. Iodine can enter water resources from various sources, including nuclear accidents, medical procedures, and natural occurrences. To address this issue, the use of natural occurring nanoporous minerals, such as zeolitic materials, for iodine removal will be explored. This study focuses on the adsorption of iodine by silver-modified zeolites (13X-Ag, 5A-Ag, Chabazite-Ag, and Clinoptilolite-Ag) and evaluates their performance under different conditions. All materials were characterized using scanning electron microscopey (SEM), energy-dispersive X-ray spectroscopy (EDS), powdered X-ray diffraction (P-XRD), Fourier-transform infrared spectrometry (FTIR), and nitrogen adsorption studies. The results indicate that Chabazite-Ag exhibited the highest iodine adsorption capacity, with an impressive 769 mg/g, making it a viable option for iodine removal applications. 13X-Ag and 5A-Ag also demonstrated substantial adsorption capacities of 714 mg/g and 556 mg/g, respectively, though their behavior varied according to different models. In contrast, Clinoptilolite-Ag exhibited strong pH-dependent behavior, rendering it less suitable for neutral to slightly acidic conditions. Furthermore, this study explored the impact of ionic strength on iodine adsorption, revealing that Chabazite-Ag is efficient in low-salinity environments with an iodine adsorption capacity of 51.80 mg/g but less effective in saline conditions. 5A-Ag proved to be a versatile option for various water treatments, maintaining its iodine adsorption capacity across different salinity levels. In contrast, Clinoptilolite-Ag exhibited high sensitivity to ionic competition, virtually losing its iodine adsorption ability at a NaCl concentration of 0.1 M. Kinetic studies indicated that the pseudo-second-order model best describes the adsorption process, suggesting chemisorption mechanisms dominate iodine removal. Chabazite-Ag exhibited the highest initial adsorption rate with a k 2 value of 0.002 mg g -1 h -1 , emphasizing its superior adsorption capabilities. Chabazite and Clinoptilolite, naturally occurring minerals, provide eco-friendly solutions for iodine adsorption. Chabazite superior iodine removal highlights its value in critical applications and its potential for addressing pressing environmental challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-scale Imaging of PGM-free Catalyst Active Sites by 30 keV 4D-STEM

Platinum group metal (PGM)-free catalysts have attracted a large amount of attention due to their potential for enabling low-cost, commercially viable hydrogen fuel cells and electrolyzers [1]. Degradation of cell performance remains a significant challenge, however, currently limiting implementation of devices that utilize PGM-free materials [2]. Controlling degradation in these materials requires a better understanding of the atomic structure of active sites, thought to be FeN4 structures within a graphitic carbon lattice, which would enable more accurate prediction of the associated degradation pathways. The exact structural arrangement of active sites in these materials is still debated since a range of structures have been computationally predicted and methods to directly validate these models are still needed [1,3-5].While scanning transmission electron microscopy (STEM) has provided initial glimpses into the nature of the proposed active sites, detailed evaluation of the structure of these sites is challenging since they involve defects, edges, and nitrogen dopants in the graphitic lattice, which are susceptible to beam damage [6,7]. Conventional STEM imaging and spectroscopy methods exacerbate this problem with dose-inefficiency or nonideal contrast characteristics for imaging light and heavy elements simultaneously. A method that minimizes damage while generating dose-efficient, easily-interpretable contrast for both light and heavy elements is therefore needed to facilitate imaging of sensitive active site atomic structure.Here, we demonstrate direct atomic-scale imaging of PGM-free catalyst active sites by low-voltage four-dimensional (4D)-STEM. To accomplish this, we pair a 30 keV aberration-corrected probe, which minimizes knock-on damage, with a fast pixelated detector that has optimal performance at low beam energies [8]. We show how this setup enables relatively simple center-of-mass (CoM) techniques [9,10] to produce images with an increased signal-to-noise ratio (SNR) and light-element contrast over conventional imaging modes, allowing the entire active site structure to be imaged at the atomic scale. Moreover, we show how electron ptychography [11,12] enables images with further improved characteristics to be obtained, for example by minimizing residual aberrations, which provides a more accurate structural representation. The increased understanding that these low-voltage 4D-STEM techniques will provide about the atomic structure of PGM-free active sites and their associated degradation pathways will facilitate rational design of next-generation materials, promoting development of low-cost hydrogen fuel cells, electrolyzers, and other energy conversion devices [13]. References:[1] U Martinez et al., Adv. Mater. 31 (2019), p. 1806545.[2] Y Shao et al., Adv. Mater. 31 (2019), p. 1807615.[3] J Kneebone et al., J. Phys. Chem. C 121, (2017), p.16283.[4] T Mineva et al., ACS Catal. 9 (2019), p. 9359.[5] J Li et al., Nat. Catal. 4 (2021), p. 10.[6] T Susi et al., ACS Nano 6 (2012), p. 8837.[7] P Zelenay and DJ Myers, US Department of Energy Hydrogen and Fuel Cells Program 2017 Annual Merit Review and Peer Evaluation Meeting, Washington, DC (2017).[8] H Ryll et al., J. Inst. 11 (2016), p. P04006.[9] K Müller et al., Nat. Commun. 5 (2014), p. 5653.[10] I Lazic et al., Ultramicroscopy 160 (2016), p. 265.[11] H Yang et al., Nat. Commun. 7 (2016), p. 12532.[12] Y Jiang et al., Nature 559 (2018), p. 343. [13] Research sponsored by the Hydrogen and Fuel Cell Technologies Office, Office of Energy Efficiency and Renewable Energy, US Department of Energy (DOE). Research was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

Zachman, Michael↗

ISS Ammonia Leak Detection Through X-Ray Fluorescence

Ammonia leaks are a significant concern for the International Space Station (ISS). The ISS has external transport lines that direct liquid ammonia to radiator panels where the ammonia is cooled and then brought back to thermal control units. These transport lines and radiator panels are subject to stress from micrometeorites and temperature variations, and have developed small leaks. The ISS can accommodate these leaks at their present rate, but if the rate increased by a factor of ten, it could potentially deplete the ammonia supply and impact the proper functioning of the ISS thermal control system, causing a serious safety risk. A proposed ISS astrophysics instrument, the Lobster X-Ray Monitor, can be used to detect and localize ISS ammonia leaks. Based on the optical design of the eye of its namesake crustacean, the Lobster detector gives simultaneously large field of view and good position resolution. The leak detection principle is that the nitrogen in the leaking ammonia will be ionized by X-rays from the Sun, and then emit its own characteristic Xray signal. The Lobster instrument, nominally facing zenith for its astrophysics observations, can be periodically pointed towards the ISS radiator panels and some sections of the transport lines to detect and localize the characteristic X-rays from the ammonia leaks. Another possibility is to use the ISS robot arm to grab the Lobster instrument and scan it across the transport lines and radiator panels. In this case the leak detection can be made more sensitive by including a focused 100-microampere electron beam to stimulate X-ray emission from the leaking nitrogen. Laboratory studies have shown that either approach can be used to locate ammonia leaks at the level of 0.1 kg/day, a threshold rate of concern for the ISS. The Lobster instrument uses two main components: (1) a microchannel plate optic (also known as a Lobster optic) that focuses the X-rays and directs them to the focal plane, and (2) a CCD (charge coupled device) focal plane detector that reads out the position and energy of the X-rays, allowing a determination of the leak location. The effective area of the detection system is approximately 2 cm(exp2) at 1 keV. The Lobster astrophysics instrument, designed for monitoring the sky for Xray transients, gives high sensitivity along with large field of view (30×30deg) and good spatial resolution (1 arc min). This offers a significant benefit for detecting ISS ammonia leaks, since the goal is to localize small leaks as efficiently as possible.

Camp, Jordan↗

Sputtered p-Type Cu x Zn 1– x S Back Contact to CdTe Solar Cells

As thin-film cadmium telluride (CdTe) solar cells gain prominence, one particular challenge is optimizing contacts and their interfaces to transfer charge without losses in efficiency. Back contact recombination is still significant and will prevent CdTe solar technology from reaching its full potential in device efficiency, and transparent back contacts have not been developed for bifacial solar technology or multijunction solar cells. To address these challenges, here we investigate sputtered Cu x Zn 1– x S as a p-type semi-transparent back contact material to thin-film polycrystalline CdTe solar cells at Cu concentrations x = 0.30, 0.45, and 0.60. This material is selected for its high hole conductivity (160–2120 S cm –1 ), wide optical band gap (2.25–2.75 eV), and variable ionization potential (approximately 6–7 eV) that can be aligned to that of CdTe. We report that without device optimization, CdTe solar cells with these Cu x Zn 1– x S back contacts perform as well as control cells with standard ZnTe:Cu back contacts. We observe no reduction in external quantum efficiency, low contact barrier heights of approximately 0.3 eV, and carrier lifetimes on par with those of baseline CdTe. These cells are relatively stable over one year in air, with V OC and efficiency of the x = 0.30 cell decreasing by only 1 and 3%, respectively. Using scanning electron microscopy and scanning transmission electron microscopy to investigate the Cu x Zn 1– x S/CdTe interface, we demonstrate that the Cu x Zn 1– x S layer segregates into a bilayer of Cu-Te-S and Zn-Cd-S, and thermodynamic reaction calculations support these findings. Despite its bilayer formation, the back contact still functions well. This investigation explains some of the physical mechanisms governing the device stack, inspires future work to understand interfacial chemistry and charge transfer, and elicits optimization to achieve higher-efficiency CdTe cells.

14 SOLAR ENERGY↗

Combined Rotating Disk Slurry Electrodeposition–Spontaneous Galvanic Displacement for Pt-M (M = Co, Ni, and Cu) Catalyst Synthesis for the Oxygen Reduction Reaction in Alkaline Media

Here, platinum-modified first-row transition-metal catalyst (M = Ni, Co, and Cu) nanoparticles on a carbon black Vulcan XC-72R (CBV) support were synthesized using rotating disk slurry electrodeposition (RoDSE) followed by spontaneous galvanic displacement (SGD) reactions. These RoDSE–SGD catalysts were evaluated for the oxygen reduction reaction (ORR) in 0.1 M KOH using rotating disk electrode techniques. The Ni and Co RoDSEs were done by using an electrochemical applied potential of -0.75 V versus the RHE and for Cu, -0.80 V versus the RHE using a CBV slurry solution containing 0.1 M KClO 4 . These metal nanoparticles on CBV (M/CBV) catalysts were modified with a Pt precursor via a spontaneous galvanic displacement (SGD) reaction, producing a Pt-M/CBV material to catalyze the ORR in an alkaline medium. High-resolution scanning transmission electron microscopy (HR-STEM) analysis indicates that the PtM/CBV samples include M clusters and Pt single atoms. The ORR characterization measurements were done under a controlled temperature (25.0 °C) and with a mass loading of 100 μg/cm 2 on a glassy carbon (GC) rotating disk electrode at 1600 rpm. The PtCo/CBV showed the highest ORR mass activity of 0.741 A/mgPt at 0.90 V versus the reversible hydrogen electrode (RHE) compared with commercial Pt/CBV. The M/CBV RoDSE catalysts were also tested for the oxygen evolution reaction (OER), and Ni/CBV provided the lowest overpotential of 450 mV at 10 mA/cm 2 disk in 0.1 M KOH.

30 DIRECT ENERGY CONVERSION↗

Future Plans in US Flight Missions: Using Laser Remote Sensing for Climate Science Observations

Laser Remote Sensing provides critical climate science observations necessary to better measure, understand, model and predict the Earth's water, carbon and energy cycles. Laser Remote Sensing applications for studying the Earth and other planets include three dimensional mapping of surface topography, canopy height and density, atmospheric measurement of aerosols and trace gases, plume and cloud profiles, and winds measurements. Beyond the science, data from these missions will produce new data products and applications for a multitude of end users including policy makers and urban planners on local, national and global levels. NASA Missions in formulation including Ice, Cloud, and land Elevation Satellite (ICESat 2) and the Deformation, Ecosystem Structure, and Dynamics of Ice (DESDynI), and future missions such as the Active Sensing of CO2 Emissions over Nights, Days and Seasons (ASCENDS), will incorporate the next generation of LIght Detection And Ranging (lidar) instruments to measure changes in the surface elevation of the ice, quantify ecosystem carbon storage due to biomass and its change, and provide critical data on CO 2 in the atmosphere. Goddard's plans for these instruments and potential uses for the resulting data are described below. For the ICESat 2 mission, GSFC is developing a micro-pulse multi-beam lidar. This instrument will provide improved ice elevation estimates over high slope and very rough areas and result in improved lead detection for sea ice estimates. Data about the sea ice and predictions related to sea levels will continue to help inform urban planners as the changes in the polar ice accelerate. DESDynI is planned to be launched in 2017 and includes both lidar and radar instruments. GSFC is responsible for the lidar portion of the DESDynI mission and is developing a scanning laser altimeter that will measure the Earth's topography, the structure of tree canopies, biomass, and surface roughness. The DESDynI lidar will also measure and predict the response of ice masses to climate change and impact on sea level. Data from the lidar will ultimately be fused with radar data products with heretofore unseen results and applications. The 3-D structure of forests is critical to understanding the impact of land use and associated landscape changes on the habitat of life forms and consequently on their biodiversity. Lidar instruments are also under development to measure trace gases in the atmospheric such as CO2 and methane. GSFC is developing an active measurement approach to determine the CO2 column density and surface pressure for the proposed ASCENDS mission. The objective of this approach is to produce data on the amounts of anthropogenic and organic CO2 in the atmosphere with sufficient accuracy to meet the needs of target users including state, federal and international users as well as policy-related legislative, regulatory, and voluntary carbon-related management groups local to international interests. In summary, NASA will continue to rely on laser remote sensing for critical climate science observations and is committed to the development of the next generation of lidar instruments for a range of applications.

Callahan, Lisa W.↗

Effect of Forest Canopy on Remote Sensing Soil Moisture at L-band

Global maps of soil moisture are needed to improve understanding and prediction of the global water and energy cycles. Accuracy requirements imply the use of lower frequencies (L-band) to achieve adequate penetration into the soil and to minimize attenuation by the vegetation canopy and effects of surface roughness. Success has been demonstrated over agricultural areas, but canopies with high biomass (e.g. forests) still present a challenge. Examples from recent measurements over forests with the L-band radiometer, 2D-STAR, and its predecessor, ESTAR, will be presented to illustrate the problem. ESTAR and 2D-STAR are aircraft-based synthetic aperture radiometers developed to help resolve both the engineering and algorithm issues associated with future remote sensing of soil moisture. ESTAR, which does imaging across track, was developed to demonstrate the viability of aperture synthesis for remote sensing. The instrument has participated several soil moisture experiments (e.g. at the Little Washita Watershed in 1992 and the Southern Great Plains experiments in 1997 and 1999). In addition, measurements have been made at a forest site near Waverly, VA which contains conifer forests with a variety of biomass. These data have demonstrated the success of retrieving soil moisture at L-band over agricultural areas and the response of passive observations at L-band to biomass over forests. 2D-STAR is a second generation instrument that does aperture synthesis in two dimensions (along track and cross track) and is dual polarized. This instrument has the potential to provide measurements at L-band that simulate the measurements that will be made by the two L-band sensors currently being developed for future remote sensing of soil moisture from space: Hydros (conical scan and real aperture) and SMOS (multiple incidence angle and synthetic aperture). 2D-STAR participated in the SMEX-03 soil moisture experiment, providing images from the NASA P-3 aircraft. Preliminary results include images of the experiment site area near Huntsville, AL that included a mixture of forest and agriculture. Changes during a rain event further illustrate the issues presented by forests. Work is continuing to reduce the 2D-STAR data and to support the two future remote sensing missions. Among the goals is to process the 2D-STAR data to create multiple looks (at the same pixel) with different incidence angles. Data in this format can be used to test algorithms for retrieving soil moisture and biomass such as are planned for SMOS. Also, the data are being processed to provide images at constant incidence angles such as will be obtained by Hydros. Although Hydros will have only one incidence angle, it will also carry an L-band radar, The goal is to use the radar to improve spatial resolution, an issue for remote sensing from space at the long wavelengths. Simultaneous observations with active and passive sensors also offers interesting prospects for treating areas of high biomass (forests) and irregular terrain and may be the challenge for the future.

LeVine, D. M.↗

Cyclic Oxidation of High-Temperature Alloy Wires in Air

High-temperature alloy wires are proposed for use in seal applications for future re-useable space vehicles. These alloys offer the potential for improved wear resistance of the seals. The wires must withstand the high temperature environments the seals are subjected to as well as maintain their oxidation resistance during the heating and cooling cycles of vehicle re-entry. To model this, the wires were subjected to cyclic oxidation in stagnant air. of this layer formation is dependent on temperature. Slow growing oxides such as chromia and alumina are desirable. Once the oxide is formed it can prevent the metal from further reacting with its environment. Cyclic oxidation models the changes in temperature these wires will undergo in application. Cycling the temperature introduces thermal stresses which can cause the oxide layer to break off. Re-growth of the oxide layer consumes more metal and therefore reduces the properties and durability of the material. were used for cyclic oxidation testing. The baseline material, Haynes 188, has a Co base and is a chromia former while the other two alloys, Kanthal A1 and PM2000, both have a Fe base and are alumina formers. Haynes 188 and Kanthal A1 wires are 250 pm in diameter and PM2000 wires are 150 pm in diameter. The coiled wire has a total surface area of 3 to 5 sq cm. The wires were oxidized for 11 cycles at 1204 C, each cycle containing a 1 hour heating time and a minimum 20 minute cooling time. Weights were taken between cycles. After 11 cycles, one wire of each composition was removed for analysis. The other wire continued testing for 70 cycles. Post-test analysis includes X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) for phase identification and morphology.

Reigel, Marissa M.↗

Submicron Thickness Characterization of Poly-Si Thin Films on Textured Surfaces by X-Ray Diffraction for Minimizing Parasitic Absorption in Poly-Si/SiO2 Passivating Contact Cells

Poly-Si/SiO2 passivating contacts have shown great potential for industry-relevant next-generation solar cells. Previous work has demonstrated an improved Jsc from dry reactive ion etching in an SF6 environment, using front metal grids as a self-aligned mask. Here, we show an effective method to measure the front poly-Si thickness on an alkaline textured surface using X-ray diffraction. The calculated thicknesses are compared with cross-section SEM analysis and Quokka simulation. We show that by thinning the front poly-Si from 200 nm to 60 nm, Jsc increases by 2.4 mA/cm2, leading to an absolute efficiency gain of 1.73%. Finally, we discuss possible reasons for the premature loss of passivation before the removal of all poly-Si.

41 EE - Solar Energy Technologies Office (EE-4S)↗