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At least 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

High-entropy halide perovskite single crystals stabilized by mild chemistry

High entropy materials are excellent candidates for a range of functional materials but traditionally require high-temperature synthetic procedures over 1000°C and complex processing techniques such as hot rolling to form. One route to address the extreme synthetic requirements for high entropy materials should involve designing crystal structures with ionic bonding networks and low cohesive energies. Here, we develop room-temperature (20°C) and low temperature (80°C) solution synthesis procedures for a new class of metal-halide perovskite high entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of the class of metal-halide perovskites, these HES single crystals are designed on the cubic Cs 2 MCl 6 (M = Zr 4+ , Sn 4+ , Te 4+ , Hf 4+ , Re 4+ , Os 4+ , Ir 4+ , or Pt 4+ ) vacancy-ordered double perovskite structure from the self-assembly of stabilized complexes in multielement inks, namely free Cs + cations and five or six different isolated [MCl6] 2- anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five- and six-elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs 2 MCl 6 crystal structure and stoichiometry maintained. In conclusion, the incorporation of various [MCl 6 ] 2- octahedral molecular orbitals disordered across the high entropy five- and six-element Cs 2 MCl 6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Elucidating the Structural and Electronic Effects of Ni and Mn Cationic Incorporation on CoOOH for Efficient Benzyl Alcohol Electrooxidation

Transition-metal oxyhydroxides such as CoOOH are promising low-cost electrocatalysts for the selective electrooxidation of organic molecules, yet the influence of ubiquitous transition-metal impurities on their performance and durability remains poorly understood. Here, we experimentally probed the individual and synergistic electrochemical and structural effects of Ni and Mn incorporations into model CoOOH electrocatalysts toward an efficient benzyl alcohol oxidation reaction (BAOR). Comprehensive electrochemical, microscopic, and spectroscopic analyses reveal that Ni incorporation enhances charge-transfer kinetics and overall activity through the formation of catalytically active Ni 3+ sites, whereas Mn exhibited a more complex but interesting role. At the early stages of operation, Mn 4+ acts as a stabilizing surface layer that mitigates catalyst degradation but partially blocks Co sites before they undergo gradual leaching. The concurrent incorporation of both Ni and Mn yields a trimetallic 2NMC@NF electrocatalyst that integrates the activity benefits of Ni with the stability conferred by Mn, achieving 92.9% benzyl alcohol conversion and 91.4% Faradaic efficiency after 24 h at 1.5 V vs RHE. These findings elucidate how trace Ni and Mn impurities, often introduced from electrolytes or external sources, can modulate the lattice and electronic structure of CoOOH, offering a design strategy for enhancing both activity and long-term stability in electrocatalytic organic oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

Coating Development for GRCop-84 Liners for Reusable Launch Vehicles Aided by Modeling Studies

The design of the next generation of reusable launch vehicles calls for using GRCop-84 copper alloy liners based on a composition invented at the NASA Glenn Research Center. Despite its considerable advantage over other copper alloys, it is expected that GRCop-84 will suffer from environmental degradation depending on the type of rocket fuels used and on thermomechanical fatigue. Applying protective coatings on GRCop-84 substrates can minimize or eliminate many of these problems and extend the operational life of the combustion liner. This could increase component reliability, shorten depot maintenance turnaround times, and lower operating costs. Therefore, Glenn is actively pursuing the development of advanced coatings technology for GRCop-84 liners. Technology is being developed in four major areas: (1) new metallic coating compositions, (2) application techniques, (3) test methods, and (4) life prediction design methodology using finite element analysis. The role of finite element analysis in guiding the coating effort is discussed in this report. Thermal analyses were performed at Glenn for different combinations of top- and bondcoat compositions to determine the temperature variation across the coated cross section with the thickness of the top coat. These calculations were conducted for simulated LH2/LO2 booster engine conditions assuming that the bond coat had a constant thickness of 50 m. The preceding graphs show the predicted temperatures at the outer surface of the top coat (hot wall), at the top-coat/bond-coat interface, at the bond-coat/GRCop-84 interface, and at the GRCop-84 cold wall as a function of top-coat thickness for Cu- 26(wt%)Cr top coat (top graph), Ni-17(wt%)Cr-6%Al-0.5%Y top coat and Cu-26%Cr bond coat, and NiAl top coat and Ni bond coat. In all cases, the temperature of the top coat at the hot wall increased with increasing top-coat thickness and with corresponding decreases in the temperatures at the two interfaces and the cold wall. These temperatures are not acutely sensitive to the thermal conductivity of the top coat when it exceeds 25 and 50 W/m/K for low and high heat flux engines. This observation is significant for two reasons. First, several different top-coat compositions can be evaluated as potential protective coatings without loss in the heat-transfer efficiency of the coated system. Second, materials with thermal conductivities less than the critical values of 25 or 50 W/m/K are more likely to act as thermal barrier coatings. The deposition of overlay coatings on GRCop-84 substrates results in the development of residual stresses. The presence of these residual stresses influences the probability of coating spallation, the thermal cycling life, and the fatigue properties of the coated substrate during use. Since it is important to understand how these stresses develop during the vacuum-plasma-spraying coating deposition process, the nature and magnitudes of the cool-down residual stresses were calculated and compared with experimentally determined values across the coated cross section of a disk specimen. The calculations were conducted assuming that the specimen cools down to room temperature from vacuum plasma-spraying temperatures of either 250 or 650 C. The effects of coating the substrate with and without grit blasting were also theoretically examined. The final graph compares the predicted and the experimental results for a GRCop-84 disk coated with about a 50- m-thick Ni bond coat and a 75- to 100- m NiAl top coat, where the curves for NASA-2 assume the presence of a prior residual stress generated by grit blasting under conditions similar to the experimental situation. The predicted cool-down in-plane stresses were compressive in both the NiAl top coat and the Ni bond coat. They were also compressive in the substrate to a depth of about 0.25 mm from the Ni/GRCop-84 interface when the vacuum-plasma-spraying temperature was low. However, using a higher plasma spraying temperaturs likely to leave the substrate under a small tensile stress to counter the compressive stresses in the bond and top coats because of the relaxation of residual stresses generated in the substrate during the grit blasting of its surface prior to spraying. These results suggest that the NiAl and Ni coatings are unlikely to spall after spraying as confirmed by the microstructural observations shown in the following photomicrograph of an as-sprayed specimen. Finally, it is noted that the calculated and experimental results are not in complete agreement, which indicates that both the experimental and modeling techniques need further refinement.

Raj, Sai V.↗
NASA NTRS1999

Microgravity Transport Phenomena Experiment (MTPE) Overview

The Microgravity Transport Phenomena Experiment (MTPE) is a fluids experiment supported by the Fundamentals in Biotechnology program in association with the Human Exploration and Development of Space (BEDS) initiative. The MTP Experiment will investigate fluid transport phenomena both in ground based experiments and in the microgravity environment. Many fluid transport processes are affected by gravity. Osmotic flux kinetics in planar membrane systems have been shown to be influenced by gravimetric orientation, either through convective mixing caused by unstably stratified fluid layers, or through a stable fluid boundary layer structure that forms in association with the membrane. Coupled transport phenomena also show gravity related effects. Coefficients associated with coupled transport processes are defined in terms of a steady state condition. Buoyancy (gravity) driven convection interferes with the attainment of steady state, and the measurement of coupled processes. The MTP Experiment measures the kinetics of molecular migration that occurs in fluids, in response to the application of various driving potentials. Three separate driving potentials may be applied to the MTP Experiment fluids, either singly or in combination. The driving potentials include chemical potential, thermal potential, and electrical potential. Two separate fluid arrangements are used to study membrane mediated and bulk fluid transport phenomena. Transport processes of interest in membrane mediated systems include diffusion, osmosis, and streaming potential. Bulk fluid processes of interest include coupled phenomena such as the Soret Effect, Dufour Effect, Donnan Effect, and thermal diffusion potential. MTP Experiments are performed in the Microgravity Transport Apparatus (MTA), an instrument that has been developed specifically for precision measurement of transport processes. Experiment fluids are contained within the MTA fluid cells, designed to create a one dimensional flow geometry of constant cross sectional area, and to facilitate fluid filling and draining operations in microgravity. The fluid cells may be used singly for bulk solutions, or in a Stokes diaphragm configuration to investigate membrane mediated phenomena. Thermal and electrical driving potentials are applied to the experiment fluids through boundary plates located at the ends of the fluid cells. In the ground based instrument, two constant temperature baths circulate through reservoirs adjacent to the boundary plates, and establish the thermal environment within the fluid cells. The boundary plates also serve as electrodes for measurement and application of electrical potentials. The Fluid Manipulation System associated with the MTA is a computer controlled system that enables storage and transfer of experiment fluids during on orbit operations. The system is used to automatically initiate experiments and manipulate fluids by orchestrating pump and valve operations through scripted sequences. Unique technologies are incorporated in the MTA for measurement of fluid properties. Volumetric Flow Sensors have been developed for precision measurement of total fluid volume contained within the fluid cells over time. This data is most useful for measuring the kinetics of osmosis, where fluid is transported from one fluid cell to another through a semipermeable membrane. The MicroSensor Array has been designed to perform in situ measurement of several important fluid parameters, providing simultaneous measurement of solution composition at multiple locations within the experiment fluids. Micromachined sensors and interface electronics have been developed to measure temperature, electrical conductivity, pH, cation activity, and anion activity. The Profile Refractometer uses a laser optical system to directly image the fluid Index of Refraction profile that exists along the MTA fluid cell axis. A video system acquires images of the RI profile over time, and records the transport kinetics that occur upon application of chemical, thermal, or electrical driving potentials. Image processing algorithms have been developed to analyze the refractometer images on a pixel by pixel basis, calibrating and scaling the measured Index of Refraction profile to correlated solution properties of interest such as density, concentration, and temperature. Additional software has been developed to compile the processed images into a three dimensional matrix that contains fluid composition data as a function of experiment time and position in the fluid cell. These data are combined with data from the other sensor systems, and analyzed in the context of transport coefficients associated with the various transport phenomena. Analysis protocols have been developed to measure the transient kinetics, and steady state distribution of fluid components that occur in response to the applied driving potentials. The results are expressed in terms of effective transport coefficients. Experiments have been performed using a variety of solutes, and results generated are that are in agreement with published transport coefficient values.

Mason, Larry W.↗
DOE OSTI2019

Optimum Planning for Inductively Charged On-Demand Automated Electric Shuttles at Greenville, South Carolina

Wireless charging technology presents perfect fits for autonomous electric vehicles for realizing a fully automated system (vehicle and charger). This paper presents a planning optimization analysis for a pilot project of in-route wireless charging infrastructure serving fixed-route on-demand shared automated electric shuttles (SAESs) at Greenville, South Carolina, USA. A single-objective non-linear integer planning optimization problem is formulated. A comprehensive cost function representing the inductively charged SAESs is developed, considering road construction, power electronics and materials, traction battery, and installation costs. The optimization problem is solved to determine the best combination of the system key design parameters (number and allocations of wireless chargers, charging power level, track length and on-board battery capacity) that show the most cost-effective solution and allow the SAESs realizing charge sustaining operation. The planning platform incorporates representative simulated traffic data (drive cycles and routes) for four SAESs at Greenville project using the Simulation of Urban Mobility (SUMO) tool. These data are fed to a vehicle powertrain model and a wireless charger power model to predict the battery power, energy and state-of-charge (SOC) profiles, which are provided to the search algorithm to assess the design objectives under specific constraints. The results indicated that implementing wireless charging at a few designated stops for fixed-route SAESs with proper design allows the vehicles realizing charge sustaining operation, infinite range and zero recharge downtime, with a significant reduction in the on-board battery (36 % ) and road coverage (69%), at minimum cost.

33 ADVANCED PROPULSION SYSTEMS↗
NASA NTRS2000

Advanced Communications Technology Satellite (ACTS) Used for Inclined Orbit Operations

The Advanced Communications Technology Satellite (ACTS) is operated by the NASA Glenn Research Center at Lewis Field 24 hours a day, 7 days a week. ACTS, which was launched in September 1993, is in its 7th year of operations, far exceeding the system s planned 2 years of operations and 4 years of designed mission life. After 5 successful years of operating as a geostationary satellite, the spacecraft s North-South stationkeeping was discontinued in August 1998. The system is now operating in an inclined orbit that increases at a rate of 0.8 /yr. With only scarce fuel remaining, operating in this mode extends the usage of the still totally functional payload. Although tracking systems are now needed on the experimenter Earth stations, experiment operations have continued with very little disruption. This is the only known geosynchronous Ka-band (30/20 GHz) spot-beam satellite operating in an inclined orbit. The project began its transition from geostationary operations to inclined operations in August 1998. This did not interrupt operations and was transparent to the experimenters on the system. For the space segment, new daily procedures were implemented to maintain the pointing of the system s narrow 0.3 spot beams while the spacecraft drifts in the North-South direction. For the ground segment, modifications were designed, developed, and fielded for the three classes of experimenter Earth stations. With the next generation of commercial satellite systems still being developed, ACTS remains the only operational testbed for Ka-band geosynchronous satellite communications over the Western hemisphere. Since inclined orbit operations began, the ACTS experiments program has supported 43 investigations by industry, Government, and academic organizations, as well as four demonstrations. The project s goals for inclined-orbit operations now reflect a narrower focus in the types of experiments that will be done. In these days of "faster, better, cheaper," NASA is seeking to gain greater relevance to the agency s mission from these experiments. One area that is of much interest both to NASA and the commercial world is the investigation of protocol issues related to the interoperability of satellites with terrestrial networks, such as Transmission Control Protocol/Internet Protocol (TCP/IP) and Asynchronous Transfer Mode (ATM) over wideband satellites. Other experiment areas of interest are supporting the U.S. Government and NASA as they begin using commercial space assets to meet their communications needs, evaluating issues related to operating a spot-beam satellite in inclined orbit, and evaluating new Ka-band hardware that requires a satellite link. ACTS is now in its last year of operations. Operations are planned through June 2000, when after 81 months of operations, this very successful spacecraft will be superorbited and made inert.

Bauer, Robert A.↗
DOE OSTI2020

Temperature and Solvent Effects on H 2 Splitting and Hydricity: Ramifications on CO 2 Hydrogenation by a Rhenium Pincer Catalyst

The catalytic hydrogenation of carbon dioxide holds immense promise for applications in sustainable fuel synthesis and hydrogen storage. Mechanistic studies that connect thermodynamic parameters with the kinetics of catalysis can provide new understanding and guide predictive design of improved catalysts. Reported here are thermochemical and kinetic analyses of a new pincer-ligated rhenium complex ( tBu POCOP)Re(CO) 2 ( tBu POCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) that catalyzes CO 2 hydrogenation to formate with faster rates at lower temperature. Because the catalyst follows the prototypical “outer sphere” hydrogenation mechanism, comprehensive studies of temperature and solvent effects on the H 2 splitting and hydride transfer steps are expected to be relevant to many other catalysts. Strikingly large entropy associated with cleavage of H2 results in a strong temperature dependence on the concentration of [( tBu POCOP)Re(CO) 2 H] – present during catalysis, which is further impacted by changing the solvent from toluene to tetrahydrofuran to acetonitrile. New methods for determining the hydricity of metal hydrides and formate at temperatures other than 298 K were developed, providing insight into how temperature can influence the favorability of hydride transfer during catalysis. These thermochemical insights guided the selection of conditions for CO 2 hydrogenation to formate with high activity (up to 364 h –1 at 1 atm or 3330 h –1 at 20 atm of 1:1 H 2 CO 2 ). In cases where hydride transfer is the highest individual kinetic barrier, entropic contributions to outer sphere H 2 splitting lead to a unique temperature dependence: catalytic activity increases as temperature decreases in tetrahydrofuran (200-fold increase upon cooling from 50 to 0 °C) and toluene (4-fold increase upon cooling from 100 to 50 °C). Furthermore, the ramifications on catalyst structure-function relationships are discussed, including comparisons between “outer sphere” mechanisms and metal–ligand cooperation mechanisms.

14 SOLAR ENERGY↗
NASA NTRS1993

Microgravity acceleration measurement environment characterization

The Space Acceleration Measurement System (SAMS) is a general-purpose instrumentation system designed to measure the accelerations onboard the shuttle Orbiter and shuttle/Spacelab vehicles. These measurements are used to support microgravity experiments and investigations into the microgravity environment of the vehicle. Acceleration measurement can be made at locations remote from the SAMS main instrumentation unit by the use of up to three remote triaxial sensor heads. The SAMS was developed by NASA's Lewis Research Center (LeRC) in support of NASA's microgravity science programs. In the past, numerous acceleration measurement systems have flown on various space missions. These systems were tailored to measure accelerations for a narrow set of requirements and were limited in bandwidth, dynamic range, and recording capability. In addition, these systems were mission-peculiar and not easily modified for other applications or missions. The result has been an inability to accurately assess the expected microgravity environment prior to a mission for a particular experiment and/or location. The prime science objective for SAMS on the SL-J mission will be to measure the accelerations experienced by a multitude of experiments in the two racks of the Japanese First Materials Processing Test (FMPT). The FMPT consists of a variety of materials science and life science experiments contained in racks no. 7 and no. 10. The SAMS data will be made available to the FMPT principal investigators after the mission for their analysis with the FMPT data. A secondary science objective for SAMS will be the characterization of the acceleration environment of the Spacelab module. This will include an analysis of the acceleration transfer function of the Spacelab module which will utilize the FMPT acceleration measurement along with measurements at the rack no. 9 structure. Another analytical effort to be undertaken is a general characterization of the acceleration environment of the Spacelab as an orbiting laboratory. These analysis efforts will be in conjunction with similar measurements and analyses on other SAMS Spacelab missions.

Delombard, Richard↗
DOE OSTI2025

Unraveling the Mechanism of Interfacial Charge Transfer and Photoresponsivity of WS 2 Quantum Dots/MoS 2 (0D–2D) Heterostructure-Based Transistors

To assess the efficacy of a mixed-dimensional van der Waals (vdW) heterostructure in modulating the optoelectronic responses of nanodevices, the charge transport properties of the transition-metal dichalcogenide (TMD)-based heterostructure comprising zero-dimensional (0D) WS 2 quantum dots (QDs) and two-dimensional (2D) MoS 2 flakes are critically analyzed. Herein, a facile strategy was materialized in developing an atomically thin phototransistor assembled from mechanically exfoliated MoS 2 and WS 2 QDs synthesized using a one-pot hydrothermal route. The amalgamated photodetectors exhibited a high responsivity of ∼8000 A/W at an incident power of 0.05 nW of white light, surpassing that of the pristine MoS 2 devices. Furthermore, the detectivity of pristine MoS 2 , which was on the order of 10 10 , increased to 10 12 Jones for the WS 2 QDs/MoS 2 heterostructure photodetector, outperforming other WS 2 -based materials. The quasiparticle band gap and density of states (DOS) are further analyzed to elucidate the photophysics of the WS 2 QD/MoS 2 hybrid assembly. The difference in the work function between MoS 2 and WS 2 QDs gives rise to an electric field across the 0D–2D interface, facilitating effective charge separation and migration and contributing to the enhancement of photoresponsivity. The analysis of optical responses using density functional theory (DFT) revealed stronger absorption and less reflection over a broader spectrum of wavelengths for the heterostructure compared to the pristine materials. The estimated optical conductivity aligns well with the experimentally predicted maximum photoresponsivity under visible light, which is attributed to the high absorbance of 2D MoS 2 . In conclusion, combining diverse spectroscopic and imaging techniques with quantum simulation provides insights that clarify the pertinence of 0D–2D TMDs in designing phototransistors.

WS2 QDs/MoS2 heterostructure↗
DOE OSTI2020

3D CFD Model Validation Using Benchmark Data of 1/16th Scaled VHTR Upper Plenum and Development of Wall Heat-Transfer Correlation For Laminar Flow

With support from the U.S. Department of Energy-Office of Nuclear Energy’s (DOE-NE’s) Nuclear Energy Advanced Modeling and Simulation (NEAMS) program, an effort has been pursued to support high-temperature gas-cooled reactor (HTGR) technology development and its modeling and simulation needs. There is a particular need for advanced modeling and simulation tools to predict thermal-fluid behavior in the nuclear reactor primary system, especially in the core and the lower and upper plena, during safety-related transients. In this report, two main such activities are presented relevant to the HTGRs: (1) three-dimensional (3D) computational fluid dynamics (CFD) validation using benchmark data from the upper plenum of Texas A&M University’s 1/16th scaled very-high-temperature gas-cooled reactor (VHTR), and (2) development of wall heat-transfer correlation for laminar flow in a wall-heated pipe. The CFD tool validation exercises can be helpful to choose the models and CFD tools to simulate and design specific components of the HTRGs such as upper plenum where jet mixing is a complex phenomenon. In a loss of forced circulation event, the laminar flow can be observed during the development of natural circulation flow. This work includes the development and validation of heat transfer correlations for laminar flow using the Nek5000 CFD code due to limited available experimental data for laminar flow conditions to guide low-order models (1D). In this report, the flow characteristics of a single isothermal jet discharging into the upper plenum was investigated using the Nek5000 Large-Eddy Simulation (LES) CFD tool. Several numerical simulations were performed for various jet-discharged Reynolds numbers ranging from 3,413 to 12,819. A grid-independent study was performed. The numerical results of mean velocity, root-mean-square fluctuating velocity, and Reynolds stress were compared against the benchmark data. Good agreement was obtained between simulated and measured data for axial mean velocities, except near the upper plenum hemisphere. The maximum predicted errors for axial mean velocities at various normalized coolant channel diameter heights of 1, 5, and 10 are 1.56%, 1.88%, and 3.82%, respectively. In addition, the predicted root-mean-square fluctuating velocity and Reynolds stress are qualitatively in agreement with the experimental data. The Nek5000 code was used to develop wall-heat transfer correlation for laminar flow in a cylindrical tube. Several simulations were performed for various Reynolds flow and wall-heat fluxes. A new heat transfer correlation was developed using data from Nek5000 simulation results and regression functions in Matlab. The developed heat transfer correlation is valid for various Reynolds flows from 200 to 2000. The predicted R² value for model fit was 0.875, which ensures that 87.5% of the model data lies on the Nek5000 data. Moreover, a machine learning (ML) tool was used to train and test the Nek5000 data. A good fit of the ML-based model was observed with the test data.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

A Sub-Electron-Noise Multi-Channel Cryogenic Skipper-CCD Readout ASIC

The MIDNA application specific integrated circuit (ASIC) is a skipper-CCD readout chip fabricated in a 65 nm LP-CMOS process that is capable of working at cryogenic temperatures. The chip integrates four front-end channels that process the skipper-CCD signal and performs differential averaging using a dual slope integration (DSI) circuit. Each readout channel contains a pre-amplifier, a DC restorer, and a dual-slope integrator with chopping capability. The integrator chopping is a key system design element in order to mitigate the effect of low-frequency noise produced by the integrator itself, and it is not often required with standard CCDs. Each channel consumes 4.5 mW of power, occupies 0.156 mm${^2}$ area and has an input referred noise of 2.7${\mu\nu}_{rms}$. It is demonstrated experimentally to achieve sub-electron noise when coupled with a skipper-CCD by means of averaging samples of each pixel. Here, sub-electron noise is shown in three different acquisition approaches. The signal range is 6000 electrons. The readout system achieves 0.2${e^{-}}$ RMS by averaging 1000 samples with MIDNA both at room temperature and at 180 Kelvin.

1/f noise↗
DOE OSTI2019

Samarium-Activated La 2 Hf 2 O 7 Nanoparticles as Multifunctional Phosphors

Recent developments in the field of designing novel nanostructures with various functionalities have pushed the scientific world to design and develop high-quality nanomaterials with multifunctional applications. Here, we propose a new kind of doped metal oxide pyrochlore nanostructure for solid-state phosphor, X-ray scintillator, and optical thermometry. The developed samarium-activated La 2 Hf 2 O 7 (LHOS) nanoparticles (NPs) emit a narrow and stable red emission with lower color temperature and adequate critical distance under near-UV and X-ray excitations. When the LHOS NPs are exposed to an energetic X-ray beam, the Sm 3+ ions situated at the symmetric environment get excited along with those located at the asymmetric environment, which results in a low asymmetry ratio of Sm 3+ under radioluminescence compared to photoluminescence. High activation energy and adequate thermal sensitivity of the LHOS NPs highlight their potential as a thermal sensor. Our results indicate that these Sm 3+ -activated La 2 Hf 2 O 7 NPs can serve as a multifunctional UV, X-ray, and thermographic phosphor

36 MATERIALS SCIENCE↗
DOE OSTI2018

Redox-Mediator-Assisted Electrocatalytic Hydrogen Evolution from Water by a Molybdenum Sulfide-Functionalized Metal–Organic Framework

The Zr 6 -based metal–organic framework NU-1000 was successfully functionalized with candidate catalysts—MoS x units—via SIM (solvothermal deposition in MOFs) of molybdenum(VI), followed by reaction with H2S gas. The structure of the material, named MoS x - SIM, was characterized spectroscopically and through a single-crystal X-ray diffraction measurement. These measurements and others established that the catalyst is monometallic, with mixed oxygen and sulfur coordination, and that it forms from a MOF-node-supported molybdenum-based cluster featuring only oxy ligands. Notably, the formal potential for the MOF-grafted complex, like that for the metal–sulfur active site of hydrogenase, is nearly coincident with the formal potential for the hydrogen couple. Its effective concentration within the mesoporous MOF is several hundred millimolar, and its porous-framework-based immobilization/heterogenization obviates the need for aqueous solubility as a condition for use as a well-defined catalyst. MoS x - SIM was evaluated as an electrocatalyst for evolution of molecular hydrogen from aqueous acid. Although the MoS x - functionalized framework exhibits catalytic behavior, the highly insulating nature of the support inhibits high electrocatalytic performance. Introduction of an archetypal redox mediator (RM), methyl viologen (MV 2+ ), resulted in more than 20-fold enhancement in its catalytic performance on a turnover frequency basis, implying efficient RM-assisted electron transfer to otherwise electrochemically non-addressable MoS x moieties. Electrochemical kinetic studies with additional viologens as mediators reveal an unexpected square-root dependence of overall reaction rate on mediator concentration, as well as sensitivity to the strength of RM •+ as a reductant. These observations, together with observations of potential-dependent H/D isotope effects and potential-dependent pH effects, provide useful insights into the catalysis mechanism and help to explain how the MOF-affixed monometallic catalyst can effectively catalyze a two-electron reduction reaction, i.e., hydrogen evolution from acidified water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Physics of Hard Spheres Experiment: Significant and Quantitative Findings Made

Direct examination of atomic interactions is difficult. One powerful approach to visualizing atomic interactions is to study near-index-matched colloidal dispersions of microscopic plastic spheres, which can be probed by visible light. Such spheres interact through hydrodynamic and Brownian forces, but they feel no direct force before an infinite repulsion at contact. Through the microgravity flight of the Physics of Hard Spheres Experiment (PHaSE), researchers have sought a more complete understanding of the entropically driven disorder-order transition in hard-sphere colloidal dispersions. The experiment was conceived by Professors Paul M. Chaikin and William B. Russel of Princeton University. Microgravity was required because, on Earth, index-matched colloidal dispersions often cannot be density matched, resulting in significant settling over the crystallization period. This settling makes them a poor model of the equilibrium atomic system, where the effect of gravity is truly negligible. For this purpose, a customized light-scattering instrument was designed, built, and flown by the NASA Glenn Research Center at Lewis Field on the space shuttle (shuttle missions STS 83 and STS 94). This instrument performed both static and dynamic light scattering, with sample oscillation for determining rheological properties. Scattered light from a 532- nm laser was recorded either by a 10-bit charge-coupled discharge (CCD) camera from a concentric screen covering angles of 0 to 60 or by sensitive avalanche photodiode detectors, which convert the photons into binary data from which two correlators compute autocorrelation functions. The sample cell was driven by a direct-current servomotor to allow sinusoidal oscillation for the measurement of rheological properties. Significant microgravity research findings include the observation of beautiful dendritic crystals, the crystallization of a "glassy phase" sample in microgravity that did not crystallize for over 1 year in 1g (Earth's gravity), and the emergence of face-centered-cubic (FCC) crystals late in the coarsening process (as small crystallites lost particles to the slow ripening of large crystallites). Significant quantitative findings from the microgravity experiments have been developed describing complex interactions among crystallites during the growth process, as concentration fields overlap in the surrounding disordered phase. Time-resolved Bragg scattering under microgravity captures one effect of these interactions quite conclusively for the sample at a volume fraction of 0.528. From the earliest time until the sample is almost fully crystalline, the size and overall crystallinity grow monotonically, but the number of crystallites per unit volume (number density) falls. Apparently nucleation is slower than the loss of crystallites because of the transfer of particles from small to large crystals. Thus, coarsening occurs simultaneously with growth, rather than following the completion of nucleation and growth as is generally assumed. In the same sample, an interesting signature appears in the apparent number density of crystallites and the volume fraction within the crystallites shortly before full crystallinity is reached. A brief upturn in both indicates the creation of more domains of the size of the average crystallite simultaneous with the compression of the crystallites. Only the emergence of dendritic arms offers a reasonable explanation. The arms would be "seen" by the light scattering as separate domains whose smaller radii of curvature would compress the interior phase. In fiscal year 1999, numerous papers, a doctoral dissertation, and the PHaSE final report were produced. Although this flight project has been completed, plans are in place for a follow-on colloid experiment by Chaikin and Russel that employs a light microscope within Glenn's Fluids and Combustion Facility on the International Space Station. PHaSE is providing us with a deeper understanding of the nure of phase transitions. The knowledge derived has added to the understanding of condensed matter. In addition, the burgeoning study of the dynamics of colloidal self-assembly may lead to the development of a range of photonic materials that control the desirable properties of light. Thus, applications of ordered colloidal structures include not only ultrastructure ceramics, but also photonic crystals and photothermal nanosecond light-switching devices. Industries dealing with semiconductors, electro-optics, ceramics, and composites stand to benefit from such advancements.

Doherty, Michael P.↗
NASA NTRSDate not supplied

Earth-Independent Medical Operations (EIMO) Concept of Operations

In contrast to the current crew health paradigm for low-Earth orbit and Lunar missions, which depends on real-time communication with Mission Control, deep-space exploration missions will require a significant shift in medical operations. This shift is driven by the constraints of operating at a considerable distance from Earth, such as resource limitations—lack of resupply, restricted mass, power, volume, and data—as well as communication delays and the inability to evacuate back to Earth during emergencies. To move toward a more self-reliant medical model, a strategy is needed to gradually increase space-based crew autonomy and reduce risks to mission success in the challenging environment of deep space. This transformative change, known as "Earth-Independent Medical Operations" (EIMO), explores the gradual transfer of medical care and decision-making from Earth-based support to space-based systems. The goal of this transition is to enhance astronaut health and performance while minimizing mission risks. EIMO requires the development of a medical system that integrates seamlessly with mission planning, vehicle and spacesuit design, and data architecture. This integration is crucial for building a robust medical infrastructure that not only safeguards astronaut well-being but also ensures overall mission success. The Human Research Program (HRP) Exploration Medical Capability (ExMC) Element has revised the EIMO model-based Concept of Operations (ConOps) which outlines an initial vision for EIMO. The ConOps, which is built on the stakeholders’ need, system goals, and objectives (NGOs), presents an array of in-mission scenarios that span a wide range of medical conditions demonstrating the system’s capabilities from basic to complex events. Developed by a multidisciplinary team of systems engineers, scientists, and clinicians within ExMC, the ConOps revision includes two new scenarios(Barotrauma and Self-Medical Management and Behavioral Health and Chronic Medical Care), and implementation of findings from EIMO technical interchange meetings that focused on data and training. The envisioned EIMO Medical System (MS) operates as a system of systems, gathering data from various sources such as reference databases, real-time wearable sensors, point-of-care diagnostics, and environmental controls. The MS also incorporates advanced training tools to support autonomous medical care, assisting the Crew Medical Officer (CMO) during medical events where Ground Support is either unavailable or communication-delayed beyond practicality. Furthermore, MS functions and capabilities were decomposed from the scenarios to establish foundational requirements for EIMO and traced to the NASA Spaceflight Human-System Standard(NASA-STD-3001, Volumes 1 and 2). These traces were performed to gain insights on the alignment of EIMO requirements with the NASA standard. This work serves as an initial recommendation to increase crew autonomy gradually and safely for Mars missions and future deep-space exploration.

medical system↗
DOE OSTI2020

Ion irradiation and modification: The role of coupled electronic and nuclear energy dissipation and subsequent nonequilibrium processes in materials

Understanding material responses to energy deposition from energetic charged particles is important for defect engineering, ion-beam processing, ion-beam analysis and modification, geologic aging, space exploration, and nuclear applications. As an incident ion penetrates a solid, its energy is transferred to electrons and to atomic nuclei of the solid. Much of this electronic energy deposition is subsequently transferred to the atomic structure via electron–phonon (e–ph) coupling, leading to local inelastic thermal spikes in which energy dissipation is influenced by the local environment. In addition, intense ionization can lead to high densities of localized electronic excitations in wide-bandgap materials and ceramics that can affect defect dynamics and atomic mobility. Specifically, energy exchange between electrons and atomic nuclei, along with localized electronic excitations, can lead to substantial competitive (ionization-induced annealing), additive (both electronic and nuclear energy depositions contributing to damage production), and synergistic (more damage than the sums of separate damage processes) effects. Although nonmonotonic effects of the e–ph coupling strength and athermal processes are demonstrated for pre-existing defects and residual damage during ion–solid interactions, there is limited understanding of when such electronic effects must be considered in atomic-scale models of damage production and evolution in a broad variety of materials. Complex ceramics and chemically disordered solid solution alloys with different constituent elements allow a systematic evaluation of defect dynamics and irradiation performance with increasing complexity. Current knowledge regarding tuning of bonding characteristics and chemical disorder to control atomic-level dynamics is reviewed. Although a lack of fundamental understanding obstructs the advancement of reliable predictions for ion beam material modification, it highlights challenges and opens research opportunities. Insights into the complex electronic and atomic correlations with extreme energy deposition will strengthen our ability to design materials and predict ion-irradiation-induced damage in a radiation environment, and they may pave the way to better control fundamental processes and design new material functionalities for advanced technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Time-domain theory of transient heat conduction in the local limit

Ultrafast and nanoscale heat conduction demands a unified theoretical framework that rigorously bridges macroscopic transport equations with microscopic material properties derived from statistical physics. Existing empirical generalizations of Fourier's law often lack a solid microscopic foundation, failing to connect observed non-Fourier behavior with underlying atomic-scale mechanisms. In this work, we present a time-domain theory of transient heat conduction rooted in Zwanzig's statistical theory of irreversible processes. Central to this framework is the time-domain transport function $\overleftrightarrow{𝑍}$⁡(𝑡) defined through equilibrium time-correlation functions of heat fluxes. This function generalizes the conventional concept of steady-state thermal conductivity, governing the transition of conduction dynamics from onset second sound type wave propagation at finite speeds to diffusion-dominated behavior across broad temporal and spatial scales. Unlike phonon hydrodynamic models that rely on mesoscopic constructs such as phonon drift velocity, our approach provides a quantitative and microscopic description of intrinsic memory effects in transient heat fluxes and applies universally to bulk materials at any temperature or length scale. By integrating atomistic-scale first-principles calculations with continuum-level macroscopic equations, this framework offers a robust foundation for numerical simulations of transient temperature fields. Furthermore, it facilitates the interpretation and design of transient thermal grating experiments using nanometer-scale heat sources and ultrafast laser systems in the extreme ultraviolet and x-ray wavelength ranges, advancing our understanding of heat dissipation dynamics.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Electron–electrophile coupled dinitrogen reduction in a cerium– meta -tetraphenolate system: a computational study

The use of lanthanide complexes for catalytic dinitrogen reduction is a new development in homogeneous catalysis. Density functional theory calculations on our recently reported cerium phenolate catalyst [K 2 Ce 2 (sol) 4 (mTP) 2 ] (mTP = {(OC 6 H 2 - 2- t Bu-4-Me) 2 CH} 2 - 1,3-C 6 H 4 ; sol = OMe 2 here; THF in the experiment) have been undertaken to elucidate the reduction, activation and silylation steps at the bound dinitrogen molecule, in the presence of the reductant, potassium metal (K 0 ) and the electrophile Me 3 SiCl (TMSCl). Out of the total of six electron reductions required to cleave the N 2 , the first two-electron reduction step was found to be highly disfavoured unless potassium cations (K + ) are included, upon which the step is rendered strongly exergonic; N–Si bond formation at the two-electron stage is predicted to be unfavourable. The three-electron-reduced N 2 -adduct is found to be at the reductive activation limit in the absence of added electrophiles, which can form N-element bonds and lower the overall charge. Added electron density beyond three-electron reduction no longer localises on N 2 , preventing formal N 2 4− formation. A pathway in which both K 0 and Me 3 SiCl work in concert was modelled, and six sequential reduction–silylation steps were calculated, showing how the N–N bond is cleaved after the third reduction, eventually releasing two equivalents of N(SiMe 3 ) 3 , and regenerating the starting complex with the highest barrier of any step being 22 kcal mol −1 . We establish alkali metal coordination and coupled electron–electrophile transfer as key factors in the design of rare-earth-mediated dinitrogen functionalisation.

Ahmad, Shahbaz [Univ. of Manchester (United Kingdo↗