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At least 1,783 records · Page 99
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Beyond Pristine Metal–Organic Frameworks: Preparation of Hollow MOFs and Their Composites for Catalysis, Sensing, and Adsorption Removal Applications

Metal–organic frameworks (MOFs) have been broadly applied to numerous domains with a substantial surface area, tunable pore size, and multiple unsaturated metal sites. Recently, hollow MOFs have greatly attracted the scientific community due to their internal cavities and gradient pore structures. Hollow MOFs have a higher tunability, faster mass-transfer rates, and more accessible active sites when compared to traditional, solid MOFs. Hollow MOFs are also considered to be candidates for some functional material carriers. For example, composite materials such as hollow MOFs and metal nanoparticles, metal oxides, and enzymes have been prepared. These composite materials integrate the characteristics of hollow MOFs with functional materials and are broadly used in many aspects. This review describes the preparation strategies of hollow MOFs and their composites as well as their applications in organic catalysis, electrochemical sensing, and adsorption separation. Finally, we hope that this review provides meaningful knowledge about hollow-MOF composites and their derivatives and offers many valuable references to develop hollow-MOF-based applied materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Multi-Task Learning of Scanning Electron Microscopy and Synthetic Thermal Tomography Images for Detection of Defects in Additively Manufactured Metals

One of the key challenges in laser powder bed fusion (LPBF) additive manufacturing of metals is the appearance of microscopic pores in 3D-printed metallic structures. Quality control in LPBF can be accomplished with non-destructive imaging of the actual 3D-printed structures. Thermal tomography (TT) is a promising non-contact, non-destructive imaging method, which allows for the visualization of subsurface defects in arbitrary-sized metallic structures. However, because imaging is based on heat diffusion, TT images suffer from blurring, which increases with depth. We have been investigating the enhancement of TT imaging capability using machine learning. In this work, we introduce a novel multi-task learning (MTL) approach, which simultaneously performs the classification of synthetic TT images, and segmentation of experimental scanning electron microscopy (SEM) images. Synthetic TT images are obtained from computer simulations of metallic structures with subsurface elliptical-shaped defects, while experimental SEM images are obtained from imaging of LPBF-printed stainless-steel coupons. MTL network is implemented as a shared U-net encoder between the classification and the segmentation tasks. Results of this study show that the MTL network performs better in both the classification of synthetic TT images and the segmentation of SEM images tasks, as compared to the conventional approach when the individual tasks are performed independently of each other.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Transmission Spectroscopy for the Warm Sub-Neptune HD 3167c: Evidence for Molecular Absorption and a Possible High-metallicity Atmosphere

We present a transmission spectrum for the warm (500−600 K) sub-Neptune HD 3167c obtained using the Hubble Space Telescope Wide Field Camera 3 infrared spectrograph. We combine these data, which span the 1.125–1.643 μm wavelength range, with broadband transit measurements made using Kepler/K2 (0.6–0.9 μm) and Spitzer/IRAC (4–5 μm). We find evidence for absorption by at least one of H{sub 2}O, HCN, CO{sub 2}, and CH{sub 4} (Bayes factor 7.4; 2.5σ significance), although the data precision does not allow us to unambiguously discriminate between these molecules. The transmission spectrum rules out cloud-free hydrogen-dominated atmospheres with metallicities ≤100× solar at >5.8σ confidence. In contrast, good agreement with the data is obtained for cloud-free models assuming metallicities >700× solar. However, for retrieval analyses that include the effect of clouds, a much broader range of metallicities (including subsolar) is consistent with the data, due to the degeneracy with cloud-top pressure. Self-consistent chemistry models that account for photochemistry and vertical mixing are presented for the atmosphere of HD 3167c. The predictions of these models are broadly consistent with our abundance constraints, although this is primarily due to the large uncertainties on the latter. Interior structure models suggest that the core mass fraction is >40%, independent of a rock or water core composition, and independent of atmospheric envelope metallicity up to 1000× solar. We also report abundance measurements for 15 elements in the host star, showing that it has a very nearly solar composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Bayesian Cross-matching of High Proper-motion Stars in Gaia DR2 and Photometric Metallicities for ∼1.7 million K and M Dwarfs

We present a Bayesian method to cross-match 5,827,988 high proper-motion Gaia sources (μ > 40 mas yr{sup −1}) to various photometric surveys: Two Micron All Sky Survey, AllWISE data release from the Wide-field Infrared Explorer (WISE) mission, Galaxy Evolution Explorer, Radial Velocity Experiment, Sloan Digital Sky Survey, and Panoramic Survey Telescope and Rapid Response System (Pan-STARRS). To efficiently associate these objects across catalogs, we develop a technique that compares the multidimensional distribution of all sources in the vicinity of each Gaia star to a reference distribution of random field stars obtained by extracting all sources in a region on the sky displaced 2′. This offset preserves the local field stellar density and magnitude distribution, allowing us to characterize the frequency of chance alignments. The resulting catalog with Bayesian probabilities >95% has a marginally higher match rate than current internal Gaia data release 2 (DR2) matches for most catalogs. However, a significant improvement is found with Pan-STARRS, where ∼99.8% of the sample within the Pan-STARRS footprint is recovered, as compared to a low ∼20.8% in Gaia DR2. Using these results, we train a Gaussian process regressor to calibrate two photometric metallicity relationships. For dwarfs of 3500 < T{sub eff} < 5280 K, we use metallicity values of 4378 stars from the Apache Point Observatory Galactic Evolution Experiment and Hejazi et al. to calibrate the relationship, producing results with a 1σ precision of 0.12 dex and few systematic errors. We then indirectly infer the metallicity of 4018 stars with 2850 < T{sub eff} < 3500 K, which are wide companions of primaries whose metallicities are estimated with our first regressor, to produce a relationship with a 1σ precision of 0.21 dex and significant systematic errors. Additional work is needed to better remove unresolved binaries from this second sample to reduce these systematic errors.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

H α Dots: Direct-method Metal Abundances of Low-luminosity Star-forming Systems

Utilizing low-luminosity star-forming systems discovered in the Hα Dots survey, we present spectroscopic observations undertaken using the Kitt Peak National Observatory 4 m telescope for 26 sources. With determinations of robust, “direct”-method metal abundances, we examine the properties of these dwarf systems, exploring their utility in characterizing starburst galaxies at low luminosities and stellar masses. We find that the Hα Dots survey provides an effective new avenue for identifying star-forming galaxies in these regimes. In addition, we examine abundance characteristics and metallicity scaling relations with these sources, highlighting a flattening of both the luminosity–metallicity (L–Z) and stellar mass–metallicity (M * –Z) relation slopes in these regimes as compared with those utilizing samples covering wider respective dynamic ranges. These local, accessible analogs to the kinds of star-forming dwarfs common at high redshift will help shed light on the building blocks that assembled into the massive galaxies common today.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2013

Is There a Metallicity Ceiling to Form Carbon Stars? - A Novel Technique Reveals a Scarcity of C-Stars in the Inner M31 Disk

We use medium-band near-infrared (NIR) Hubble Space Telescope WFC3 photometry with model NIR spectra of Asymptotic Giant Branch (AGB) stars to develop a new tool for efficiently distinguish- ing carbon-rich (C-type) AGB stars from oxygen-rich (M-type) AGB stars in galaxies at the edge of and outside the Local Group. We present the results of a test of this method on a region of the inner disk of M31, where we nd a surprising lack of C stars, contrary to the ndings of previous C star searches in other regions of M31. We nd only 1 candidate C star (plus up to 6 additional, less certain C stars candidates), resulting in an extremely low ratio of C to M stars (C=M = (3.3(sup +20)(sub - 0.1) x 10(sup -4)) that is 1-2 orders of magnitude lower than other C/M estimates in M31. The low C/M ratio is likely due to the high metallicity in this region which impedes stars from achieving C/O > 1 in their atmospheres. These observations provide stringent constraints to evolutionary models of metal-rich AGB stars and suggest that there is a metallicity threshold above which M stars are unable to make the transition to C stars, dramatically affecting AGB mass loss and dust production and, consequently, the observed global properties of metal-rich galaxies.

Metallicity↗
NASA NTRS2013

The Metallicity Evolution of Low Mass Galaxies: New Contraints at Intermediate Redshift

We present abundance measurements from 26 emission-line-selected galaxies at z approx. 0.6-0.7. By reaching stellar masses as low as 10(exp 8) M stellar mass, these observations provide the first measurement of the intermediate-redshift mass-metallicity (MZ) relation below 10(exp 9)M stellar mass. For the portion of our sample above M is greater than 10(exp 9)M (8/26 galaxies), we find good agreement with previous measurements of the intermediate-redshift MZ relation. Compared to the local relation, we measure an evolution that corresponds to a 0.12 dex decrease in oxygen abundances at intermediate redshifts. This result confirms the trend that metallicity evolution becomes more significant toward lower stellar masses, in keeping with a downsizing scenario where low-mass galaxies evolve onto the local MZ relation at later cosmic times. We show that these galaxies follow the local fundamental metallicity relation, where objects with higher specific (mass-normalized) star formation rates (SFRs) have lower metallicities. Furthermore, we show that the galaxies in our sample lie on an extrapolation of the SFR-M∗ relation (the star-forming main sequence). Leveraging the MZ relation and star-forming main sequence (and combining our data with higher-mass measurements from the literature), we test models that assume an equilibrium between mass inflow, outflow, and star formation.We find that outflows are required to describe the data. By comparing different outflow prescriptions, we show that momentum, driven winds can describe the MZ relation; however, this model underpredicts the amount of star formation in low-mass galaxies. This disagreement may indicate that preventive feedback from gas heating has been overestimated, or it may signify a more fundamental deviation from the equilibrium assumption.

Low Mass↗
NASA NTRS2016

Metallic Hydrogen: A Game Changing Rocket Propellant

The objective of this research is to produce metallic hydrogen in the laboratory using an innovative approach, and to study its metastability properties. Current theoretical and experimental considerations expect that extremely high pressures of order 4-6 megabar are required to transform molecular hydrogen to the metallic phase. When metallic hydrogen is produced in the laboratory it will be extremely important to determine if it is metastable at modest temperatures, i.e. remains metallic when the pressure is released. Then it could be used as the most powerful chemical rocket fuel that exists and revolutionize rocketry, allowing single-stage rockets to enter orbit and chemically fueled rockets to explore our solar system.

Metallic↗
NASA NTRSDate not supplied

Adaptation of Metal Additive Manufacturing Processes for the International Space Station

The In-Space Manufacturing (ISM) project at NASA Marshall Space Flight Center, in a partnership with the company, Made in Space, has previously investigated 3D printing of polymer materials on-orbit. In recent years, the project has begun exploring the potential for metal additive manufacturing (AM) on future space missions to reduce logistics and enable point-of-use manufacturing for sparing and repair. This paper provides an overview of constraints for demonstrating a manufacturing process on the International Space Station (ISS) as well as information on previous trades of available metal AM processes and their potential for in-space use. There are currently two processes in development as payloads for an ISS technology demonstration: wire+arc additive manufacturing (the Vulcan payload from Made in Space, Inc.) and bound metal additive manufacturing (the Fabrication Laboratory from Techshot, Inc). An update on both of these systems, key results to date, and future development efforts will be presented. Relevant modeling work, performed by NASA Ames Research Center, to evaluate operation of certain aspects of the bound metal AM process in a microgravity environment will also be summarized.

in-space manufacturing↗
NASA NTRS2021

Analysis of Nonlinear Shrinkage for the Bound Metal Deposition Manufacturing using Multi-scale Approach

We consider problem of nonlinear shrinkage of the metal part during bound metal deposition manufacturing on the ground and in zero-G. To analyze this problem we developed multi-scale physics-based approach that spans atomistic dynamics at the scale of nanoseconds and the full part shrinkage at the time scale of hours. Using this approach we estimated the key parameters of the problem including grain boundary width, coefficient of surface diffusion, initial redistribution of particles during debinding stage, micro-structure evolution from round particles to densely packed grains and corresponding change of the total and chemical free energy, and sintering stress. The introduced method was used to predict shrinkage at the level of two particles, filament cross-section, sub-model, and the whole green, brown, and metal parts. To further improve accuracy and reliability of the shrinkage predictions we propose concept of intelligent additive manufacturing of metal powders in space that combines the strengths of both physics-based and data-driven methods of analysis of AM.

bound metal deposition↗
NASA NTRS2022

Elevated Hot Gas and High-mass X-Ray Binary Emission in Low-metallicity Galaxies: Implications for Nebular Ionization and Intergalactic Medium Heating in the Early Universe

High-energy emission associated with star formation has been proposed as a significant source of interstellar medium (ISM) ionization in low-metallicity starbursts and an important contributor to the heating of the intergalactic medium (IGM) in the high-redshift (z ≳ 8) universe. Using Chandra observations of a sample of 30 galaxies at D ≈ 200–450 Mpc that have high specific star formation rates of 3–9 Gyr^(−1) and metallicities near Z ≈ 0.3Z_⊙, we provide new measurements of the average 0.5–8 keV spectral shape and normalization per unit star formation rate (SFR). We model the sample-combined X-ray spectrum as a combination of hot gas and high-mass X-ray binary (HMXB) populations and constrain their relative contributions. We derive scaling relations of log L^(HMXB)_(0.5-8keV) / SFR = 40.19 ± 0.06 and log L^(gas)_(0.5-2keV) / SFR = 39.58 ^(+0.17)_(-0.28), significantly elevated compared to local relations. The HMXB scaling is also somewhat higher than L^(HMXB)_(0.5-8keV) -SFR-Z relations presented in the literature, potentially due to our galaxies having relatively low HMXB obscuration and young and X-ray luminous stellar populations. The elevation of the hot gas scaling relation is at the level expected for diminished attenuation due to a reduction of metals; however, we cannot conclude that an L^(gas)_(0.5-2keV) -SFR-Z relation is driven solely by changes in ISM metal content. Finally, we present SFR-scaled spectral models (both emergent and intrinsic) that span the X-ray-to-IR band, providing new benchmarks for studies of the impact of ISM ionization and IGM heating in the early universe.

high-mass x-ray binary stars↗
DOE OSTI2021

Development of Bismuth and Platinum Bi-Metallic Nanoparticles to Enhance Melt Wire Temperature Resolution

Advanced manufacturing (AM) based on direct-write (DW) technologies has emerged as the predominant enabler for the fabrication of active and passive sensors to be deployed in harsh operating environments seen in a nuclear reactor. Recently, Idaho National Laboratory and Boise State University have recently established capabilities to incorporate advanced manufacturing (AM) methods to accelerate, modernize and enhance functionality of nuclear sensors and instrumentation to achieve the goal of enhancing the safety and efficiency of nuclear reactors. A significant thrust of this work includes the development of nuclear relevant feedstock materials compatible with a variety of direct-write processes for the development, fabrication and testing of AM sensors for peak temperature detection and neutron flux monitoring. For this report, bismuth and bismuth/platinum (BiPt) bi-metallic nanoparticles were synthesized using wet chemical approaches to develop bi-metallic feedstock materials to enhance the sensitivity of melt wires for peak temperature detection. Nanoparticle characterization was performed with Transmission Electron Microscopy (TEM) for nanoparticle composition and size, Transmission X-Ray Diffraction Fluorescence (TXRF) for nanoparticle composition, and Differential Scanning Calorimetry to elucidate the melting point of BiPt bi-metallic nanoparticles. Preliminary results indicate bi-metallic BiPt nanoparticles as a viable pathway for fabricating high resolution AM melt wires.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Understanding Solid-Electrolyte Interphase Formation at the Lithium Metal Anode of Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are one of the most promising chemistries for the next generation of energy storage devices. In a standard Li-S cell, the metallic lithium anode is an essential component of the battery due to its low density, extremely high theoretical specific capacity, and very low negative electrochemical potential. However, several challenges related to the use of Li metal have prevented this battery technology from becoming commercially available. For instance, Li-anodes are highly reactive, which results in the continuous decomposition of the electrolyte and the formation of the solid-electrolyte interphase (SEI) layer. This, combined with the non-uniform deposition of Liions during plating at the anode surface, can seriously affect the performance, cycling, and safety of the battery. In addition, it has been suggested that a controlled SEI formation at the metallic Li anode can yield enhanced battery performance. Hence, a comprehensive understanding of how the SEI layer is formed can help elucidate improvements in this battery technology. In this work, the formation of the SEI layer in Li-S batteries is investigated using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The stability of liquid organic-based electrolyte components, salt concentration, electron-rich environments, and the use of inorganic solid-state electrolyte (SSE) materials are explored in order to provide molecular-level fundamental insights into how the nature and composition of the electrolyte can alter the initial stages of the SEI formation. The products of electrolyte decomposition and electro-/chemical reaction pathways of liquid electrolyte component such as solvent and salts are predicted from AIMD simulations of electrolyte-anode interfaces. Energetics of reactions from DFT ground-state optimizations are also presented to confirm the decomposition mechanisms. Some significant differences are then drawn regarding the use of low and high salt concentrations. Simulations under electron-rich environments show additional multielectron electrochemical reactions of solvent and salt decomposition taking place due to the excess of electrons and the presence of radical anions in the solution. Finally, the initial stages of formation, stability, and main constituents of interfaces between Li-metal and Sbased electrodes with sulfide-based SSEs are characterized in detail.

25 ENERGY STORAGE↗
DOE OSTI2026

Metallic Fuels Beyond SFRs

Metallic nuclear fuels have traditionally been used for sodium cooled fast reactor applications, but recent work has been done in applying metal fuel technologies to the light water reactor and molten salt reactor spaces. This presentation offers a brief history of metallic fuel use in SFRs and an overview of metallic fuel uses in the LWR and MSR spaces.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Silver-carbon-nanotube composite metallization for increased durability of silicon solar cells against cell cracks

One of the ways to reduce the cost of solar electricity is to reduce the degradation rate of solar modules and extend their lifetime well beyond 30 years. The extended module lifetime translates to increased bankability of utility-scale PV projects. In this work, we specifically address cell-crack-induced degradation by introducing crack-tolerant metallization. Herein, we make use of low-cost, multi-walled carbon nanotubes embedded in commercial screen-printable silver pastes as a highly integratable engineering solution. When the carbon nanotubes are appropriately functionalized and incorporated into commercial silver pastes, the resulting metal contacts on solar cells, after screen-printing and firing, show exceptional fracture toughness. These composite metal contacts possess increased ductility, electrical gap-bridging capability greater than 50 µm, and “self-healing” to regain electrical continuity even after cycles of complete electrical failure under large strain. While providing crack-tolerant mechanical properties, the composite paste delivers similar beginning-of-life cell performance as the conventional silver paste.

14 SOLAR ENERGY↗
DOE OSTI2024

Ceramic–Metal (Cermet) Composites: A Review of Key Properties and Synthesis Methods Focused on Nuclear Waste Immobilization

Here this paper reviews key properties, applications, and examples of ceramic-metal composites (cermets), and metal matrix composites (MMC) with emphasis on their applicability as waste forms for immobilizing nuclear waste. While the literature is mature for vitrified and cementitious radioactive waste forms, cermet materials have not received adequate attention as potential candidates for immobilizing nuclear waste. To promulgate this effort, this review connects cermet and MMC design, such as hardened tools, with the chemistry of radioactive waste streams. A discussion on certification and qualification standards for cermet waste forms, literature gaps, and “how-to” sections on cermet processing techniques. Key parameters discussed include thermal conductivity, chemical durability, and waste loading, as well as examples for metal-containing waste forms. As cermet waste forms gain momentum within the community, this review paper aims ensure the end-of-life nuclear fuel cycle is addressed from a materials and waste disposition perspective.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cu-, Co-, and Zn-Based Metal–Organic Framework-Derived Nanoporous Ion Emitters for Picogram Level Analysis of Actinides

Thermal ionization mass spectrometry (TIMS) is often regarded as the preferred technique for trace-level isotopic analysis of actinides owing to its high sensitivity and absence of carry-over effects. However, actinide sample utilization efficiency (SUE) is typically low (<0.05%) without the use of activators or specialized loading approaches which can yield SUEs of >5%. To this effect, we investigate a series of metal–organic framework (MOF)-based nanoporous ion emitters (nano-PIEs) that show enhanced ionization of actinides when used in TIMS loading. We study the impact of physical and chemical properties of MOFs on TIMS SUEs using two families of MOFs that can be synthesized under similar reaction conditions. The structural and chemical properties of these MOFs can be systematically modified one at a time while keeping other features the same. This allows us to strategically investigate their impact on SUEs. The first family of MOFs considered in this study is Zeolitic Imidazole Frameworks (ZIFs) which are made using 2 methyl-imidazole as an organic linker with zinc (ZIF-8) and cobalt (ZIF-67) as metal centers. Additionally, the effect of morphology was also studied using Zn-based ZIF-L with a 2-dimensional structure. The second family of MOFs was synthesized using benzene-1,3,5-tricarboxylate (BTC) with copper (Cu-BTC) and zinc (Zn-BTC) as the metal center. Among the MOFs tested, Cu-BTC showed the highest SUE with an average SUE of 0.27 ± 0.15%, followed closely by Zn-BTC (0.24 ± 0.10%), ZIF-8 (0.17 ± 0.10%), and trailed by the other MOFs. When the MOFs were pyrolyzed in N 2 before loading, an apparent increase in the SUE was observed with ZIF-8 and Cu-BTC showing average SUEs of 0.25 ± 0.08% and 0.34 ± 0.13%, respectively, with the highest measured SUE of 0.53% for pyrolyzed Cu-BTC. In conclusion, this observed increase in SUE by up to an order of magnitude compared to bare filaments demonstrates the efficacy and potential of MOF-derived nano-PIEs for TIMS application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Photo-induced Charge Separation and Photoredox Catalysis in Cerium-Based Metal–Organic Frameworks

Separation of photo-induced charges (electrons and holes) can exert important control over the lifetimes of photo-excited states. Such separation may be promoted in Metal–Organic frameworks (MOFs), which are organic–inorganic hybrid materials, through ligand-to-metal charge transfer (LMCT). Here, in this chapter, we discuss our recent work on photocatalysis with Ce-based MOFs, which feature LMCT due to the low-lying empty 4f states of Ce(IV). We discuss the electronic structure of Ce-based UiO-66, the effects of linker functionalization and metal (Zr or Ti) doping on the electronic structure of Ce-based UiO-66, and the photoredox possibilities of the selected Ce-MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗