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800 records · Page 44

High-Order Methods in NASA’s Next Generation of Computational Fluid Dynamics Tools

The missions of the National Aeronautics and Space Administration (NASA) routinely produce unique requirements and challenges for development and application of Computational Fluid Dynamics (CFD) methods. NASA presently embodies four distinct Mission Directorates: Aeronautics Research, Exploration Systems, Science, and Space Operations. These missions generate requirements for systems that operate in a wide variety of environments. They range from the high-speed flight of aerodynamically optimized vehicles operating in the earth’s atmosphere to spacecraft designed for missions that don’t favor aerodynamic optimization, some operating in the atmosphere of planets and planetary moons such as Mars and Venus or Saturn’s moon Titan. Systems supporting these vehicles, such as rocket and jet propulsion, reaction control systems, fluid and thermal transfer systems, etc. can also generate their own unique set of flow phenomena that challenge today’s CFD methodology. Through the NASA Engineering and Safety Center (NESC), NASA annually conducts state-of-the-discipline assessments in fifteen distinct engineering disciplines. These assessments are performed by the NASA Technical Fellows that lead Technical Discipline Teams (TDT) of recognized experts in these fifteen areas. In the Aerosciences discipline, three topics have been identified as the top challenges for the discipline: aero-plume interaction prediction, unsteady separated flows, and aerothermodynamic prediction. These challenge areas are defined by the Agency’s high-risk projects and problems on which the NESC is requested to perform independent testing, analysis, and assessments. When viewed as a whole, these tests, analyses, and assessments provide a clear view of the recurring technical challenges facing Agency engineers and researchers and can be used to guide future research and technology development. The present state-of-the-art in the application of CFD at NASA is the use of Reynolds-Averaged Navier- Stokes (RANS) solvers, primarily executed in a steady-state mode of operation. In isolated cases, Unsteady RANS (URANS) solvers have been employed when steady RANS solutions produce poorly converging or oscillating results or in cases, such as aeroelastic analysis, which require unsteady aerodynamic simulation. For most traditional external and internal aerodynamic flows, structured overset grids or unstructured grids are employed to minimize geometric modeling and grid generation times. Grid adaptation, primarily as a series of coarse-grain intermediate processing steps is also seeing use on particularly complex flow problems and configurations. In the case of aerothermodynamic flows, engineers have been forced to continue to employ structured grid techniques as the present unstructured grid methodology has proven inadequate in the prediction of surface heating. In the area of aero-plume interaction modeling, two-gas, frozen chemistry simulation is generally the state-of-the- art, with some production solvers capable of predicting flows with only a single gas component. Prediction of flows falling into the afore-mentioned top Aerosciences technical challenges have severely stressed the present state-of-the-art in CFD prediction and for some problems, such as unsteady separated flows and aero-plume interaction cases, engineers have begun employing Large Eddy Simulation (LES) and Hybrid RANS/LES techniques. In some isolated aero-propulsion interaction cases, chemically reacting flow simulations have been applied. These methods are highly evolutionary and engineers have little experience in their application, so they cannot be heavily relied upon in today’s application environment. Therefore, this leads one to muse over which numerical technologies will be included in the CFD tools that will be employed 30 years in the future. This presentation will describe specific technical problems that have stressed NASA’s traditional CFD methods to their breaking point and will link these issues to the Agency’s top Aerosciences technical challenges. The discussion will then shift to the characteristics of future CFD solvers that will be required to attack these challenges and how these characteristics differ from the present state-of-the- art. High-order methods certainly appear to have a place in the development of future CFD tools and some of the physical characteristics of our most challenging problems suggest that high-order methods are the only way to effectively solve them. But there are some relatively severe implementation issues that face these methods, particularly in the area of general applicability and robust operation as an engineering tool. Desired characteristics of next-generation CFD solvers will be discussed and the author’s view of which emerging numerical technologies might be employed to address these attributes will also be presented

David M Schuster

Preliminary Assessment of the Impact on the V-Band Oxygen Channels From Satellite Communication Uplinks

We calculate the percentage of time that an ATMS-like instrument [1] will be illuminated by the uplink beam of one of the proposed V-band communication system and estimate the damage resulting from such exposure. Using a combination of openly available information and educated guesses about the location and characteristics of the up/down link terminals, we constructed the ground segment of a hypothetical high-speed communication network. The space segment of the network was constructed from the orbital data of the existing Starlink constellation [2] of 6223 communication satellites (comsats) which is used as strawman to represent any other possible constellation of communication satellites. It is shown that without a very delicate balance of frequency allocations (science vs telecommunications), coupled with extremely steep and deep bandpass-defining filters, and strict adherence to the agreed limits (i.e. no out-of-band transmissions) the deployment of the telecommunication network leads to almost-complete loss of some important geophysical data. For the analysis we use the spectral characteristics of the ATMS instrument with the ephemeris for the NOAA-21 satellite [3]. The analysis is conducted for the USA and the simulation covers 8 consecutive days in July 2024. Effective and accurate microwave remote sensing of the atmosphere depends on the availability of interference-free spectrum windows at frequencies which are prescribed by physical processes [e.g. 4]. The family of resonant lines of the oxygen molecule near 60 GHz provides a unique opportunity to sample the vertical distribution of temperature and density from space, and it has been exploited for weather and climate studies from polar-orbiting satellites since 1978 (MSU on TIROS-N [5]). It remains a staple in the payloads operated by Russia, China, USA, Japan, France, India, UK, Ukraine [6] which are built around a common blueprint: a few wide-band (hundreds of MHz) channels around 50 GHz to sample the atmosphere and the surface while several more channels with high spectral resolution (few MHz) sample the individual resonant lines. Accurate retrieval of the environmental parameters depends upon the data provided by both sets of channels, and the their location in frequency space is not arbitrary and cannot be altered at will [7, 8]. The introduction of 5G technology in 2019 has driven telecommunication companies to request more bandwidth to be dedicated to their devices. This additional bandwidth is only available in spectral regions traditionally reserved for environmental and astrophysical research, such as the V-band between 50 and 60 GHz for up/downlink between satellites in low-earth orbits and terminals connected to fiberoptics network for distribution to high-speed local internet services. The power broadcast by the uplink communication leg is many orders of magnitude greater than the natural thermal signal emitted from the Earth scene. If the ground antenna were to perfectly align with the passive instrument’s antenna, the spaceborne receiver would suffer permanent, irreparable damage. While a direct boresight-to-boresight conjunction is extremely unlikely (even with a large constellation of satellites the fraction of the celestial sphere occupied by the satellites remains minuscule) the finite size of the ground station’s antenna beam in the sky suggests that the ATMS will be in the near background (as seen from the ground station) of one of the communication satellites and will be illuminated by either the main lobe or the near sidelobes of the uplink antenna more often than it is desirable. For our analysis we first calculate the position of the ATMS with respect to each of the ground stations at a resolution of 0.2 sec, then calculate the position of each of the comsats which are at least 25 deg above the station’s local horizon; finally we calculate the angle between the line-of-sight of the ATMS and the line-of-sight of the comsat. We assume that the gain pattern of the ground station is circularly symmetric; the angle-off-station-boresight then provides an attenuation of the uplink power which we use to assess the likely effect upon the passive instrument’s operations. We assume that each ground station can communicate with all the comsats in its field of view; this implies that, on average, a ground station can engage with 46 comsats simultaneously. The analysis is repeated for the case when the uplink broadcast within the ATMS passive channels (in-band scenario) and for the case when the uplink is limited to frequencies adjacent to the ATMS channels (out-of-band scenario). The antenna of the ground station is modelled as having a HPBW (Half-Power Beam Width) of 0.16 deg and EIRP (Equivalent Isotropic Radiated Power) of 70 dBW. We account for the geometric dissipation of the signal caused by the satellite orbital altitude, the attenuation induced by atmospheric gasses at 51 GHz and the mismatch between the circular polarization of the ground-based transmitting antenna and the linear polarization of the satellite-borne receiving antenna. The damages on ATMS are estimated from bench-level measurement conducted at the ATMS’ manufacturer facilities [unpublished].

passive microwave

An integrated in-situ coordination strategy enabling high-performance layered cathodes for sodium-ion batteries

O3-type layered transition metal oxide cathodes hold tremendous potential in sodium-ion batteries (SIBs) due to their low cost and high energy density. However, the structure instability associated with detrimental phase transitions and severe interface parasitic reactions exacerbate the material's electrochemical performance degradation. Herein, we develop an integrated in-situ coordination strategy via heteroatomic modulation inducing coherent epitaxial layer to collaboratively enhance the overall framework robustness from surface to bulk. The theoretical calculation and multiple in/ex-situ characterizations demonstrate the charge density around oxygen is redistributed, which promotes the electron localization, thus widening the NaO 2 lattice space and accelerating the Na + transport dynamics. Furthermore, the formed strengthened oxygen bond energy effectively distributes the long-range coordination of Mn 3+ O 6 octahedron, thereby alleviating Jahn-Teller distortion and local stress. Importantly, the in-situ formed conformal buffer layer dramatically relieves the adverse interface side reactions, facilitating the construction of robust cathode-electrolyte interface, which ameliorate the whole structure stability of designed materials. Consequently, the optimized NFMZ@NZO-1.0 exhibits the excellent cycling stability with 80.2% capacity retention after 300 cycles at 1C, and delivers a high discharge capacity of 107.1 mAh g −1 at 10C. In conclusion, this distinctive coupling strategy provides valuable insights for developing high-performance layered cathode materials in SIBs.

Coherent epitaxial layer

Extreme confinement of hydrogen gas within fullerenelike nanoporous carbon

Nanoporous carbons and carbon nanostructures can store hydrogen at cryogenic temperatures but lack the volumetric and gravimetric capacity to be industrially significant. Recent inelastic neutron scattering experiments suggest a highly dense phase of hydrogen at temperatures well above the melting point of solid hydrogen. However, it remains unclear how pore geometry and intermolecular interactions enable these dense phases to exist, with dispersion (van der Waals) or electrostatic/induction suggested to be the key effects in slit and curved pores but their relative contributions have yet to be quantified. In this paper, we perform benchmark electronic structure calculations allowing the interactions between planar and curved aromatic molecules with hydrogen to be accurately determined. Dispersion was found to dominate over electrostatic and inductive effects with some many-body charge transfer (Dobson type-A) effects needed to capture the most highly curved structures. Density functional methods that include type-A many-body effects were found to accurately describe the intermolecular interactions at a fraction of the cost of coupled-cluster simulations and these approaches were used to calculate the energies inside large carbon bowl and slit pores. The interaction energies inside the bowl pores were found to depend on the orientation of the hydrogen molecule. This rotational barrier, modeled as a quantum hindered rotor, could reproduce the peak splitting observed in inelastic neutron scattering experiments, with weak splitting arising from bowl-like fullerene pores and strong splitting from highly confining nanotubelike pores. Increasing the fraction of such curved pores in nanoporous carbons may therefore offer a pathway to enhance their hydrogen-storage capacity. Moreover, the preferential adsorption of ortho hydrogen on nanotubelike pores could enable the storage of high-density hydrogen without the need to remove heat produced during the ortho-para hydrogen conversion.

36 MATERIALS SCIENCE

Heliostat sizing methodology for concentrating solar thermal industrial process heat projects

This study presents a method to obtain a heliostat size that minimizes the levelized cost of heat (LCOH) of a heliostat-based concentrating solar thermal system for applications of solar heating for industrial processes at operating temperatures from 565 to 1550°C. The method extends prior work by embedding a routine for system design that obtains near-optimal subsystem sizes, increasing the fidelity of drive cost functions, and adding an optical performance model to supplement the previously developed cost models, which we update to reflect current pricing trends. An illustrative business case is developed for Daggett, California, targeting specified annual thermal energy outputs of 50 to 400 GWh th . Optical performance is modeled using verified estimates from the literature. A surrogate heliostat cost model, derived from commercial heliostat designs and scaled for production volume, installation, and operations and maintenance costs, is used to develop cost functions. Results show that heliostat size strongly affects the LCOH, producing a characteristic U-shaped trend with a robust near-optimal window of 7-20 m 2 ; the heliostat size producing the lowest project cost in our study grows slightly as the project size increases, and is reduced as the operating temperature increases. The findings in this study are consistent with the general trend of smaller heliostats being deployed at existing projects for high-temperature industrial process heat and reflect the significant reduction in power electronics and other per-heliostat costs. The methodology we propose is general and can be tailored to revised cost curves as the technology continues to evolve.

14 SOLAR ENERGY

High-Precision Shape Control of In-Space Deployable Large Membrane/Thin-Shell Reflectors

This innovation has been developed to improve the resolutions of future spacebased active and passive microwave antennas for earth-science remote sensing missions by maintaining surface figure precisions of large membrane/thin-shell reflectors during orbiting. The intention is for these sensing instruments to be deployable at orbit altitudes one or two orders of magnitude higher than Low Earth Orbit (LEO), but still being able to acquire measurements at spatial resolution and sensitivity similar to those of LEO. Because active and passive microwave remote sensors are able to penetrate through clouds to acquire vertical profile measurements of geophysical parameters, it is desirable to elevate them to the higher orbits to obtain orbital geometries that offer large spatial coverage and more frequent observations. This capability is essential for monitoring and for detailed understanding of the life cycles of natural hazards, such as hurricanes, tropical storms, flash floods, and tsunamis. Major components of this high-precision antenna-surface-control system include a membrane/thin shell reflector, a metrology sensor, a controller, actuators, and corresponding power amplifier and signal conditioning electronics (see figure). Actuators are attached to the back of the reflector to produce contraction/ expansion forces to adjust the shape of the thin-material reflector. The wavefront-sensing metrology system continuously measures the surface figure of the reflector, converts the surface figure to digital data and feeds the data to the controller. The controller determines the control parameters and generates commands to the actuator system. The flexible, piezoelectric polymer actuators are thus activated, providing the control forces needed to correct any distortions that exist in the reflector surface. Piezoelectric polymer actuators are very thin and flexible. They can be implemented on the back of the membrane/thin-shell reflector without introducing significant amounts of mass or stiffness to the reflector. They can be rolled up or folded to accommodate the packaging needed for launch. An analytical model of the system, which includes the membrane reflector, actuator, and controller has been developed to investigate the functionality of this control system on a 35-meter-diameter membrane reflector. The performance of this system under external disturbances such as in space thermal loads and W-error due to inflation has been investigated. A subscale breadboard has been developed, and the functionality of this control concept has been demonstrated by this breadboard.

Houfei Fang

Innovations Driven by Advanced Characterization to Strategize Critical Mineral Production and Beneficial Reuse from Fossil Energy Waste

Critical minerals (CM), such as rare earth elements (REE), cobalt, nickel, and lithium, have important uses in modern electronics and advanced manufacturing, yet are vulnerable to potential supply chain disruptions. Relatively abundant and readily available fossil energy (FE) wastes, such as coal combustion ash, acid mine drainage (AMD) and treatment solids (AMD solids), and Oil and Gas (O&G) drilling wastes (drill cuttings and produced waters) are under consideration as CM feedstocks. The National Energy Technology Laboratory (NETL) has studied CM resources for various FE wastes as part of the U.S. Department of Energy’s mission of bolstering the domestic CM supply, and makes the data available to the public on EDX at sites such as the NEWTS group. Advanced characterization utilizing synchrotron x-ray techniques coupled with laboratory extractions has been performed to identify CM hosting phases in these FE wastes to inform CM recoverability mechanisms. Novel methods to selectively recover CMs while co-producing other valuable byproducts have been developed. Successful examples discussed here include: (1) The identification of REE/Co/Ni/Sc binding and hosting phases in select FE waste (coal combustion ash and AMD solids), resulting in the development of a patented CM step-extraction process, (2) coupled production of functional sorbents from these extraction wastes and for CM recovery. A pilot-scale testing to evaluate the patent’s technical feasibility for extracting REE from coal ash on a barrel scale has been successfully performed. Additionally, (3) evaluation and measurements of brine geochemistry from U.S. O&G produced waters has informed a high Li recovery potential from Marcellus Shale produced water. NETL researchers have been developing tailored pre-treatment processes, an innovative and highly durable lithium sorbent, and geochemical model guided precipitation to accelerate Li production from the Marcellus Shale produced waters. These innovations driven by characterization are integral for maximizing and advancing the potential for CM recovery while offsetting the cost and environmental footprint for FE waste management.

critical mineral processing

Hund's coupling governed orbital-selective superconductivity in Ba 1−𝑥 ⁢K 𝑥⁢ Fe 2 ⁢As 2

Understanding how strong electronic correlations shape superconductivity remains a central challenge in quantum materials. In multiorbital systems, correlations driven by Hund's coupling can differentiate the behavior of individual orbitals, producing the so-called Hund's metal state. How such orbital-selectivity also governs superconducting pairing, however, has remained largely unexplored experimentally. Here, in this study, we use high-resolution angle-resolved photoemission spectroscopy to systematically map the superconducting gap structure across the phase diagram of the representative iron-based superconductor Ba 1−x K x Fe 2 As 2 . We find that superconductivity evolves in a strongly orbital-dependent manner: the gap associated with the d xy orbital collapses beyond optimal doping while pairing on the d xz /d yz orbitals persists. This behavior mirrors the orbital-selective correlations observed in the normal state and reveals a direct connection between Hund's metal physics and the superconducting pairing landscape. Our results demonstrate that superconducting gaps themselves can serve as a sensitive probe of orbital-dependent correlations and suggest that Hund's coupling plays a central role in shaping pairing in multiorbital superconductors.

Corbae, Elena [SLAC National Accelerator Laborator

Review on Preprocessing Strategies, Deactivation, Thermal Safety, and Future Perspectives in Lithium-Ion Battery Recycling

The rapid growth in the use of lithium-ion batteries (LIBs) in electric vehicles, consumer electronics, and renewable energy storage has made effective end-of-life management essential. Recycling LIBs is critical not only for resource recovery and environmental protection but also for ensuring safety and economic viability. This review focuses on the preprocessing technologies that precede typical recovery processes, including disassembly, sorting, discharging, electrolyte removal, dismantling, thermal treatment, separation, and flotation. These steps play a foundational role in determining the efficiency, safety, and environmental impact of LIB recycling. LIBs pose substantial fire and explosion risks due to residual charge, flammable electrolytes, and reactive materials. The conditions and successive progression of the exothermic reactions which lead to thermal runaway has been discussed. It also explores secure deactivation techniques such as external circuit discharge, saline immersion, and thermomechanical methods, alongside fire prevention strategies including the use of flame retardants, elimination of oxidants, and reduction of heat generation and accumulation. Challenges and future directions are outlined, highlighting the need for standardized designs, automation, and safer, more sustainable recycling infrastructure. Furthermore, this review is distinguished by its focused analysis of preprocessing and deactivation steps, with particular attention to the thermal safety engineering aspects of LIB recycling.

Battery deactivation

Metrology for femtosecond pulsed x-ray heating in diamond anvil cell experiments at the European XFEL: Revisiting the iron phase diagram up to 150 GPa

The development of pulsed intense x-ray sources, such as free electron laser, offers new avenues for high pressure experiments. Here, we study the feasibility and metrology of x-ray heating in diamond anvil cells at the European x-ray free electron laser. This method enables one to volumetrically heat the sample while inhibiting chemical migration and probing the crystallographic structure of the sample throughout the heating with a high repetition rate. We focus our study on iron, whose phase diagram is well established up to 100 GPa, to explore the possibilities and limitations of this technique. We volumetrically heat iron samples at starting pressures ranging from 10 to 138 GPa, using the x-ray beam pulsed at 4.5 MHz in a serial pump-and-probe experimental design. Experimental challenges arise from temperature gradients within the sample, changes in temperature at the 100 ns timescale, the difficulty of direct temperature estimates, the effect of thermal pressure, and the presence of metastable crystallites due to rapid cycles of heating and cooling. Hence, we develop a multi-crystal-like data processing method that allows us to account for sample heterogeneity in probed conditions. We then calibrate our measurements using known physical properties of iron under pressure. Thermal pressure in our experiments increases from 4% of the isochoric prediction at 10 GPa to 23% at 138 GPa, and we show that our data are in agreement with most previous observations of iron in this pressure range. The method can now be implemented at higher pressures and temperatures and on materials with unknown phase diagrams.

Materials science

Using Open Innovation in Reducing Risk to Crews

In the exploration of destinations outside of Earth's neighborhood, specifically Mars, scientific and engineering inquiries have occurred by two means; observations from satellites and observations by landed spacecraft. Satellite observations (Mariner, MRO, Mars Odyssey, provide global-scale spatial and temporal data while landed spacecraft (Viking, Mars Pathfinder, Spirit, Opportunity, Phoenix Mars Lander) investigate highly localized areas of the surface of the planet. In preparation for human exploration, extensive knowledge of the surface and atmospheric environments should be known before the first human leaves Earth. The primary goal of performing reconnaissance on Mars on a sub-global scale is to know as much as possible about the environment to which crews will be subjected. At the current rate of launching and landing probes to Mars, it will take a very long time to understand the surface and atmospheric conditions associated with the regions where prospective crews may land. Meanwhile electronics and electrical systems are rapidly getting smaller. One can argue that to acquire the knowledge of the region, one must take hundreds, maybe thousands of measurements simultaneously. One means to perform such a task is to deploy a swarm of sensors. Such a swarm would perform an in-situ assessment of the region. Imagine a close flyby mission to Mars for example, where mini- to micro-sensors are deposited into the atmosphere over half an orbit or more. The sensors, captured by the atmospheric drag and Martian gravity slowly descend buffeted about by Martian winds and weather until they settle on the surface a great time later (think of how long dust takes to settle). As they descend they communicate a vast array of data; temperature, chemistry, pressure, radiation dose, electric or magnetic properties from a region of the planet and an individual sensor need not measure the same quantity as its neighbors. Initially, they could move at the whim of the environment but later versions could have locomotion or propulsion mechanisms. Humans wouldn't need to decide where the sensors go, the sensors do that for themselves. This is a key strength of a sensor swarm. The intelligence relies on the group not on a decision maker on earth. Real time sensor inputs direct what the swarm considers most interesting to investigate resulting in emergent behavior. We issued a $20,000 challenge to the global innovators to provide solutions as to how such a swarm could be initialized and by what protocols and methodologies by which they operate. Over 400 innovators from 49 countries took a look at the problem, with three receiving partial awards for solutions.

Mel Ferebee

Radiation-induced alteration of apatite on the surface of Mars: first in situ observations with SuperCam Raman onboard Perseverance

Abstract Planetary exploration relies considerably on mineral characterization to advance our understanding of the solar system, the planets and their evolution. Thus, we must understand past and present processes that can alter materials exposed on the surface, affecting space mission data. Here, we analyze the first dataset monitoring the evolution of a known mineral target in situ on the Martian surface, brought there as a SuperCam calibration target onboard the Perseverance rover. We used Raman spectroscopy to monitor the crystalline state of a synthetic apatite sample over the first 950 Martian days (sols) of the Mars2020 mission. We note significant variations in the Raman spectra acquired on this target, specifically a decrease in the relative contribution of the Raman signal to the total signal. These observations are consistent with the results of a UV-irradiation test performed in the laboratory under conditions mimicking ambient Martian conditions. We conclude that the observed evolution reflects an alteration of the material, specifically the creation of electronic defects, due to its exposure to the Martian environment and, in particular, UV irradiation. This ongoing process of alteration of the Martian surface needs to be taken into account for mineralogical space mission data analysis.

Science & Technology - Other Topics

Elimination of detrimental grain boundary segregation in garnets

Garnet Li 7 La 3 Zr 2 O 12 electrolyte is considered a key enabler of solid-state batteries with Li metal electrodes, but the grain boundaries impair its performance. To date, the understanding of grain boundary structures and its impact on performance remains elusive. Here, we show that element segregation at Li 7 La 3 Zr 2 O 12 grain boundaries critically governs Li transport and nucleation. During conventional sintering, Al, Ta, and La segregate at grain boundaries, locally depleting Li and creating space-charge layers that lower total ionic conductivity. Simultaneously, this segregation leads to higher electronic conductivity along grain boundaries, which promotes Li nucleation at grain boundary edges with increased risk of dendrite formation. The underlying mechanism of segregation is governed by both thermodynamic driving forces and diffusion kinetics. Building on this understanding, we develop a strategy to achieve segregation-free grain boundaries through a rapid sintering protocol that utilizes the onset of solid-state softening. This approach yields transparent, polycrystalline Li 7 La 3 Zr 2 O 12 with negligible grain boundary impedance and enhanced dendrite tolerance. By elucidating the structural origins and electrochemical consequences of grain boundary segregation, this work provides a guidance for the rational optimization of solid electrolytes.

Energy - Storage

Remote-Contact Catalysis for Target-Diameter Semiconducting Carbon Nanotube Arrays

Electrostatic catalysis has been an exciting development in chemical synthesis (beyond enzymes catalysis1 ) in recent years, boosting reaction rates and selectively producing certain reaction products2 . Most of the studies to date have been focused on using external electric field (EEF) to rearrange the charge distribution in small molecule reactions such as Diels-Alder addition3 , carbene reaction4 , etc. However, in order for these EEFs to be effective, a field on the order of 1 V/nm (10 MV/cm) is required, and the direction of the EEF has to be aligned with the reaction axis5 . Such a large and oriented EEF will be challenging for large-scale implementation, or materials growth with multiple reaction axis or steps. Here, we demonstrate that the energy band at the tip of an individual single-walled carbon nanotube6 (SWCNT) can be spontaneously shifted in a high-permittivity growth environment, with its other end in contact with a low-work function electrode (e.g., hafnium carbide or titanium carbide7 ). By adjusting the Fermi level at a point where there is a substantial disparity in the density of states (DOS) between semiconducting (s-) and metallic (m-) SWCNTs8 , we achieve effective electrostatic catalysis for s-SWCNT growth assisted by a weak EEF perturbation (200V/cm). This approach enables the production of high-purity (99.92%) s-SWCNT horizontal arrays with narrow diameter distribution (0.95±0.04 nm), targeting the requirement of advanced SWCNT-based electronics for future computing9-11. These findings highlight the potential of electrostatic catalysis in precise materials growth, especially for s-SWCNTs, and pave the way for the development of advanced SWCNT-based electronics12.

Wang, Jiangtao [Department of Electrical Engineeri

Structural and spectroscopic characterization of a Tb(IV) polyoxometalate

There has been a renaissance in high valent lanthanide chemistry, which has resulted in the first examples of tetravalent praseodymium (Pr) and terbium (Tb) in molecular systems. These feats have been achieved with tailored ligands that facilitate tetravalent lanthanide stability in non-aqueous conditions. The next step in realizing the potential of high valent lanthanide chemistry is moving towards complexes that are stable in ambient and aqueous conditions. In this investigation, we advance this paradigm by obtaining definitive evidence of Tb(IV) in a molecular system under aqueous conditions utilizing the lacunary Wells-Dawson polyoxometalate, K 10 P 2 W 17 O 61 •20H 2 O. Herein we present the single crystal structure of K 16 Tb(IV)(P 2 W 17 O 61 ) 2 •39.85H 2 O (Tb(IV)W 34 ) as well as extensive spectroscopic evidence obtained via UV–Vis-NIR, X-ray absorption near edge spectroscopy, continuous wave X-band electron paramagnetic resonance spectroscopy and SQUID magnetometry measurements to confirm the oxidation state of Tb in W 34 complexes as +4.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

General Purpose Data-Driven Monitoring for Space Operations

As modern space propulsion and exploration systems improve in capability and efficiency, their designs are becoming increasingly sophisticated and complex. Determining the health state of these systems, using traditional parameter limit checking, model-based, or rule-based methods, is becoming more difficult as the number of sensors and component interactions grow. Data-driven monitoring techniques have been developed to address these issues by analyzing system operations data to automatically characterize normal system behavior. System health can be monitored by comparing real-time operating data with these nominal characterizations, providing detection of anomalous data signatures indicative of system faults or failures. Data-driven techniques have a number of advantages over other methods for monitoring complex space vehicles. Unlike model-based systems, the developer does not need to understand or encode the internal operation of the system. The knowledge required to monitor the system is automatically derived from archived data from system operation. Unlike rule-based systems, data-driven systems do not require system analysts to define nominal relationships among sensors. Analysts can and often do determine these relationships for a system with few sensors; it is more difficult to analytically determine the nominal relationship among a large number of sensors. Data-driven techniques are not limited to low-dimensional spaces and work as effectively with dozens of parameters as they do with a few. Knowledge bases formed by data-driven techniques are also easy to update. As the operating envelope of the monitored system is expanded, data-driven techniques can be quickly retrained to incorporate the new behavior into the knowledge base. The expertise and time-consuming process of updating a model or rule base to maintain consistency with the new operation is not required. The Inductive Monitoring System (IMS) is a data-driven system health monitoring software tool that has been successfully applied to several aerospace applications. IMS uses a data mining technique called clustering to analyze archived system data and characterize normal interactions between parameters. This characterization, or model, of nominal operation is stored in a knowledge base that can be used for real-time system monitoring or analysis of archived events. System data is compared with the nominal IMS model to produce a measure of how well current system behavior matches the normal behavior defined by the training data. Significant deviations from the nominal system model can provide alerts to system malfunctions or precursors of significant failures. The scope of IMS based data-driven monitoring applications continues to expand with current development activities. Successful IMS deployment in the International Space Station (ISS) flight control room to monitor ISS attitude control systems has led to applications in other ISS flight control disciplines, such as thermal control. It has also generated interest in data-driven monitoring capability for Constellation, NASA's program to replace the Space Shuttle with new launch vehicles and spacecraft capable of returning astronauts to the moon, and then on to Mars. Several projects are currently underway to evaluate and mature the IMS technology and complementary tools for use in the Constellation program. These include an experiment on board the Air Force TacSat-3 satellite, and ground systems monitoring for NASA's Ares I-X and Ares I launch vehicles. The TacSat-3 Vehicle System Management (TVSM) project is a software experiment to integrate fault and anomaly detection algorithms and diagnosis tools with executive and adaptive planning functions contained in the flight software on-board the Air Force Research Laboratory TacSat-3 satellite. The TVSM software package will be uploaded after launch to monitor spacecraft subsystems such as power and guidance, navigation, and control (GN&C). It will analyze data in real-time to demonstrate detection of faults and unusual conditions, diagnose problems, and react to threats to spacecraft health and mission goals. The experiment will demonstrate the feasibility and effectiveness of integrated system health management (ISHM) technologies with both ground and on-board experiments. Initially, the TVSM software will run open loop, providing system health information and recommendations to ground operators, without automatically performing fault-mitigating corrective actions. After the end of the satellite's mission, closed loop tests combining TVSM monitoring and diagnosis with reactive capabilities by the flight software will be performed. In addition to monitoring for long periods of actual operation, the experiment will include fault injection into TacSat-3 data as well as commanded operations to test and evaluate automatic ISHM monitoring and recovery under controlled conditions.

Satellites

Aliovalent gallium dopants remove Ti 3+ defects and improve photocatalytic and photoelectrochemical water oxidation properties of LaTiO 2 N

LaTiO 2 N is a promising semiconductor for the water splitting reaction due to its 2.1 eV band gap and stability against corrosion. However, its solar energy conversion is limited by Ti 3+ recombination defects introduced during ammonolysis. Here we show for the first time that Ti 3+ defects in LaTiO 2 N can be suppressed with incorporation of 2, 5, and 10% aliovalent gallium (Ga 3+ ) dopants during synthesis via the layered La 2 Ti 2 O 7 intermediate. Electron paramagnetic resonance (EPR) spectroscopy on the solid powders confirms a reduction in the Ti 3+ donor density from 2.97 × 10 17 cm −3 for the non-doped material to ∼6.24 × 10 16 cm −3 for 5% Ga-doped LaTiO 2 N. The remaining Ti 3+ defects are concentrated near the LaTiO 2 N surface, according to X-ray photoelectron spectroscopy. The defect reduction shifts the optical absorption edge from 2.02 to 2.09 eV and eliminates a broad absorption band at 1050 nm from the optical absorption spectra. It also removes a 1.0–1.7 eV sub-band gap photovoltage signal from surface photovoltage spectra. This suggests that empty Ti 3+ d-orbitals are located 1.0–1.7 eV above the LaTiO 2 N valence band edge. Removing these recombination states with increasing Ga 3+ content enhances the photoconversion efficiency of LaTiO 2 N during water oxidation. The optimized 2 wt% CoO x -loaded 5% Ga-doped LaTi O2 N material has a 16% AQE (400 nm) for O 2 production from aqueous silver nitrate solution and a ∼2.1 mA cm −2 water oxidation photocurrent at 1.23 V under 100 mW cm −2 Xe arc lamp illumination. The water oxidation photocurrent is stable during a 50 min test, and the Faraday efficiency for O 2 generation is 97%, confirming short-term corrosion stability of LaTiO 2 N. Altogether, these results provide a better understanding of the distribution, concentration, and impact of Ti 3+ defects on the optical, photovoltage, and photoelectrochemical properties of LaTiO 2 N. In combination with other defect control strategies, aliovalent Ga 3+ doping can help bring the solar energy conversion efficiency of LaTiO 2 N closer to the theoretical limit.

Wang, Li [University of California, Davis, CA (Uni

Chapter 19B - Antenna Radiation Patterns

Modern civil and military aircraft are equipped with a variety of communication devices, radio navigation equipment, and air traffic control systems. For all of these devices appropriate antennas must be available to transmit and receive the signals. As a result, as many as 30 antennas, and sometimes even more, are mounted around today's aircraft. For this reason, it is necessary to know the capabilities of the receiving/transmitting equipment on board. These capabilities are driven by the antenna characteristics. Therefore, coverage, shading, and beam pointing pattern data are necessary for optimum electronic coverage. The aircraft antenna has to convert the available power density of the electromagnetic field to an electric voltage at its connector. This voltage level must be sufficiently high to operate the connected equipment. The reciprocity principle states that it makes no difference if the antenna is receiving or transmitting. For the certification of the aircraft antennas it must be proven that the antennas are at least generating the minimum receiver input voltage which is required for each radio service. The prime condition is, of course, that the specified field power densities of the different radio navigation and communication services are available. An important property of a radio frequency link is the electro-magnetic field intensity at every point in space for a given output power of the antenna. As the propagation of radio frequency waves in free space is well known, the spatial distribution of the field intensity needs only be measured at one spatial sphere around the antenna. The information is usually given as distributions along the circumference of flat sections through this sphere: each of these is called an ARP. Several ARPs are usually required to describe the complete spatial antenna pattern of an antenna. In addition to mathematical modeling, measurements on sub-scale models, and static measurements on full size models or aircraft on the ground, dynamic measurements on aircraft in flight play the most important role in the aircraft antenna testing and certification. [19B-1] The shape of an ARP, for one given frequency, is determined by the shape of the antenna and the shape and material of the surface it is mounted on. As the directly transmitted waves interfere with waves reflected by the aircraft skin with its complex geometry, and the surface material parameters are only roughly known, it is not possible to predict the ARP with the required accuracy. In ground measurements the earth's surface also acts as a reflector thereby causing the ground ARP to be different from the in-flight ARP. As the in-flight ARP is the ARP we are actually interested in it becomes clear that it is necessary to conduct in-flight ARP measurements. The Flight Test Engineer must be aware of the needs of the specialists who are establishing the test program for measuring antenna patterns and radar cross sections. These tests will require special test equipment and dedicated flights to obtain the data that they require. This Section provides an introduction to the principles of determining antenna patterns and the flight techniques for determining both antenna patterns and radar cross section. Reference 19B-1 provides detailed information.

Helmut Bothe