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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition

An experimental investigation into the growth of polyurea films by molecular layer deposition was performed by examining trends in the growth rate, crystallinity, and orientation of chains as a function of backbone flexibility. Growth curves obtained for films containing backbones of aliphatic and phenyl groups indicate that an increase in backbone flexibility leads to a reduction in growth rate from 4 to 1 Å/cycle. Crystallinity measurements collected using grazing incidence X-ray diffraction and Fourier transform infrared spectroscopy suggest that some chains form paracrystalline, out-of-plane stacks of polymer segments with packing distances ranging from 4.4 to 3.7 Å depending on the monomer size. Diffraction intensity is largely a function of the homogeneity of the backbone. Near-edge X-ray absorption fine structure measurements for thin and thick samples show an average chain orientation of ~25° relative to the substrate across all samples, suggesting that changes in growth rate are not caused by differences in chain angle but instead may be caused by differences in the frequency of chain terminations. In conclusion, these results suggest a model of molecular layer deposition-based chain growth in which films consist of a mixture of upward growing chains and horizontally aligned layers of paracrystalline polymer segments.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Integration of molecular-layer-deposited aluminum alkoxide interlayers into inorganic nanolaminate barriers for encapsulation of organic electronics with improved stress resistance

Diffusion barrier stacks for the encapsulation of organic electronics made from inorganic nanolaminates of Al{sub 2}O{sub 3} and TiO{sub 2} with aluminum alkoxide interlayers have been deposited by atomic layer deposition (ALD) and molecular layer deposition (MLD). As a part of the MLD process development, the deposition of aluminum alkoxide with low a density of about 1.7 g/cm{sup 3} was verified. The ALD/MLD diffusion barrier stack is meant to be deposited either on a polymer film, creating a flexible barrier substrate, or on top of a device on glass, creating a thin-film encapsulation. In order to measure the water vapor transmission rate (WVTR) through the barrier, the device is replaced by a calcium layer acting as a water sensor in an electrical calcium test. For the barrier stack applied as thin-film encapsulation on glass substrates, high resolution scanning electron microscopy investigations indicate that the inorganic nanolaminates without MLD interlayers are brittle as they crack easily upon the stress induced by the corroding calcium below. The introduction of up to three MLD interlayers of 12 nm each into the 48 nm barrier film laminate successfully mitigates stress issues and prevents the barrier from cracking. Using the three MLD interlayer configurations on glass, WVTRs of as low as 10{sup −5} g/m{sup 2}/d are measured at 38 °C and 32% relative humidity. On polymer barrier substrates, the calcium is evaporated onto the barrier stack and encapsulated with a cavity glass. In this configuration, the corroding calcium has space for expansion and gas release without affecting the underlying barrier film. In consequence, a WVTR of about 3 × 10{sup −3} g/m{sup 2}/d is measured for all samples independently of the number of MLD interlayers. In conclusion, a stabilization and preservation of the ALD barrier film against mechanical stress is achieved by the introduction of MLD interlayers into the inorganic nanolaminate.

36 MATERIALS SCIENCE↗
DOE OSTI2016

SU-F-T-665: Confocal Microscopy Imaging of Cell Cycle Distribution in Cells Treated with Pegylated Gold Nanoshells

Purpose: To use confocal microscopy to distinguish cells in different phases of the cell cycle before and after treatment with pegylated gold nanoshells (PEG-AuNSs). Methods: Transfected fibrosarcoma cells (HT1080-EYFP-53BP1-FUCCI) were cultured in T-25 flasks and seeded in glass bottom dishes. These cells express the fluorescent probe AmCyan during the G2/S phases of the cell cycle, mCherry during the G1 phase, and EYFP tagged to the DNA repair protein 53BP1. After allowing cells 4 h to adhere to dishes, PEG-AuNS (Nanospectra Biosciences, Houston, TX) at a concentration of 0.15 OD were administered. At time points of 8, 16 and 24 h following treatment, the PEG-AuNS-treated and control samples were washed with phosphate buffered saline (PBS) and fixed using 4% paraformaldehyde in PBS. Samples were imaged with an Olympus FV1200 confocal microscope using 473, 543, and 641 nm excitation lasers. We used band-pass filters to select AmCyan and mCherry fluorescence. Reflection from the 641 nm laser was used to detect PEG-AuNSs. Z-stack images were analyzed to assess cell cycle distribution through fluorescent probe expression. Live cells were imaged after PEG-AuNS treatment using a confocal microscope with a stage top CO2 incubator. Results: We were able to obtain high-resolution images of cells with internalized AuNSs. We were also able to distinguish cells in different phases of the cell cycle. Conclusion: This work demonstrates a new assay to investigate the effect of AuNSs on the cell cycle phase in live cells. Future work will employ confocal microscopy and flow cytometry to focus on effects of AuNS treatment on cell cycle distribution. This research was supported by the Sister Institution Network Fund and the Center for Radiation Oncology Research at The University of Texas MD Anderson Cancer Center and Cancer Prevention and Research Institute of Texas. Gabriel Sawakuchi has research support from Elekta Inc.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2012

STACKED REST-FRAME ULTRAVIOLET SPECTRA OF Ly{alpha}-EMITTING AND CONTINUUM-SELECTED GALAXIES AT 2 < z < 3.5

We present properties of individual and composite rest-UV spectra of continuum- and narrowband-selected star-forming galaxies (SFGs) at a redshift of 2 < z < 3.5 discovered by the MUSYC collaboration in the Extended Chandra Deep Field-South. Among our sample of 81 UV-bright SFGs, 59 have R < 25.5, of which 32 have rest-frame equivalent widths of W{sub Ly{alpha}} > 20 A, the canonical limit to be classified as an Ly{alpha}-emitting galaxy. We divide our data set into subsamples based on properties that we are able to measure for each individual galaxy: Ly{alpha} equivalent width, rest-frame UV colors, and redshift. Among our subsample of galaxies with R < 25.5, those with rest frame W{sub Ly{alpha}} > 20 A have bluer UV continua, weaker low-ionization interstellar absorption lines, weaker C IV absorption, and stronger Si II* nebular emission than those with W{sub Ly{alpha}} < 20 A. We measure a velocity offset of {Delta}v {approx} 600 km s{sup -1} between Ly{alpha} emission and low-ionization absorption, which does not vary substantially among any of our subsamples. We find that the interstellar component, as opposed to the stellar component, dominates the high-ionization absorption line profiles. We find that the low- and high-ionization Si ionization states have similar kinematic properties, yet the low-ionization absorption is correlated with Ly{alpha} emission and the high-ionization absorption is not. These trends are consistent with outflowing neutral gas being in the form of neutral clouds embedded in ionized gas as previously suggested by Steidel et al. Moreover, our galaxies with bluer UV colors have stronger Ly{alpha} emission, weaker low-ionization absorption, and more prominent nebular emission line profiles. From a redshift of 2.7 < z < 3.5 to 2.0 < z < 2.7, our subsample of galaxies with W{sub Ly{alpha}} < 20 Angstrom-Sign shows no significant evolution in their physical properties or the nature of their outflows. Among our data set, UV-bright galaxies with W{sub Ly{alpha}} > 20 A exhibit weaker Ly{alpha} emission at lower redshifts, although we caution that this could be caused by spectroscopic confirmation of low Ly{alpha} equivalent width galaxies being harder at z {approx} 3 than z {approx} 2.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Investigation of properties of CdSeTe/Sb and Sb/CdSeTe stacks

The effect of Sb inclusion in CdSeTe thin films was examined. CdSeTe alloys were grown by co-evaporation, either on 5 nm thick electron-beam evaporated Sb layers (Sb/CdSeTe) or coated with Sb post-deposition (CdSeTe/Sb). Sb inclusion improved CdSeTe grain structure, a critical factor for device performance, with average grain size increasing from 0.6 to 1.5 μm. All samples crystallized on annealing to the cubic structure, with a change in film orientation from (111) to random or (220). The presence of Sb in CdSeTe/Sb or Sb/CdSeTe samples, however, had a limited effect on the carrier concentration compared to Sb-free samples. Time resolved photoluminescence showed Sb inclusion increased decay lifetimes, with τ1 = 0.8 ns for and τ2 = 6.9 ns for the Sb/CdSeTe sample.

14 SOLAR ENERGY↗
DOE OSTI2011

VARIABILITY AND MULTIWAVELENGTH-DETECTED ACTIVE GALACTIC NUCLEI IN THE GOODS FIELDS

We identify 85 variable galaxies in the GOODS North and South fields using five epochs of Hubble Space Telescope Advance Camera for Survey V-band (F606W) images spanning 6 months. The variables are identified through significant flux changes in the galaxy's nucleus and represent {approx}2% of the survey galaxies. With the aim of studying the active galaxy population in the GOODS fields, we compare the variability-selected sample with X-ray and mid-IR active galactic nucleus (AGN) candidates. Forty-nine percent of the variables are associated with X-ray sources identified in the 2Ms Chandra surveys. Twenty-four percent of X-ray sources likely to be AGNs are optical variables and this percentage increases with decreasing hardness ratio of the X-ray emission. Stacking of the non-X-ray-detected variables reveals marginally significant soft X-ray emission. Forty-eight percent of mid-IR power-law sources are optical variables, all but one of which is also X-ray detected. Thus, about half of the optical variables are associated with either X-ray or mid-IR power-law emission. The slope of the power-law fit through the Spitzer IRAC bands indicates that two-thirds of the variables have BLAGN-like spectral energy distributions. Among those galaxies spectroscopically identified as AGNs, we observe variability in 74% of broad-line AGNs and 15% of NLAGNs. The variables are found in galaxies extending to z{approx} 3.6. We compare the variable galaxy colors and magnitudes to the X-ray and mid-IR sample and find that the non-X-ray-detected variable hosts extend to bluer colors and fainter intrinsic magnitudes. The variable AGN candidates have Eddington ratios similar to those of X-ray-selected AGNs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Strongly Anisotropic Thermomechanical Response to Shock Wave Loading in Oriented Samples of the Triclinic Molecular Crystal 1,3,5-Triamino-2,4,6-trinitrobenzene

All-atom molecular dynamics (MD) simulations were used to study shock wave loading in oriented single crystals of the highly anisotropic triclinic molecular crystal 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). The crystal structure consists of planar hydrogen-bonded sheets of individually planar TATB molecules that stack into graphitic-like layers. Shocks were studied for seven systematically prepared crystal orientations with limiting cases that correspond to shock propagation exactly perpendicular and exactly parallel to the graphitic-like layers. The simulations were performed for initially defect-free crystals using a reverse-ballistic configuration that generates explicit, supported shocks. Final longitudinal stress components are between ≈8.5 and ≈10.5 GPa for the 1.0 km s –1 impact speed studied. Orientation-dependent properties are reported including shock speeds, stresses, temperatures, compression ratios, and local material strain rates. Spatiotemporal maps of the temperature, stress tensor, material flow, and molecular orientations reveal complicated processes that arise for specific shock directions. Furthermore, the results indicate that TATB shock response is highly sensitive to crystal orientation, with significant qualitative differences for the time evolution of the stress tensor and temperature, elastic/inelastic compression response, defect formation and growth, critical von Mises stress, and strain rates during shock rise that span nearly an order of magnitude. A variety of inelastic deformation mechanisms are identified, ranging from crumpling of graphitic-like layers to dislocation-mediated plasticity to intense shear strain localization. To our knowledge, these are the first systematic MD simulations and analysis of explicit shock wave propagation along nontrivial crystal directions in a triclinic molecular crystal.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Materials Learning Algorithms (MALA): Scalable machine learning for electronic structure calculations in large-scale atomistic simulations

We present the Materials Learning Algorithms (MALA) package, a scalable machine learning framework designed to accelerate density functional theory (DFT) calculations suitable for large-scale atomistic simulations. Using local descriptors of the atomic environment, MALA models efficiently predict key electronic observables, including local density of states, electronic density, density of states, and total energy. The package integrates data sampling, model training and scalable inference into a unified library, while ensuring compatibility with standard DFT and molecular dynamics codes. We demonstrate MALA's capabilities with examples including boron clusters, aluminum across its solid-liquid phase boundary, and predicting the electronic structure of a stacking fault in a large beryllium slab. Scaling analyses reveal MALA's computational efficiency and identify bottlenecks for future optimization. With its ability to model electronic structures at scales far beyond standard DFT, MALA is well suited for modeling complex material systems, making it a versatile tool for advanced materials research.

Density functional theory↗
DOE OSTI2011

DEEP SPITZER OBSERVATIONS OF INFRARED-FAINT RADIO SOURCES: HIGH-REDSHIFT RADIO-LOUD ACTIVE GALACTIC NUCLEI?

Infrared-faint radio sources (IFRSs) are a rare class of objects which are relatively bright at radio wavelengths but very faint at infrared and optical wavelengths. Here we present sensitive near-infrared observations of a sample of these sources taken as part of the Spitzer Extragalactic Representative Volume Survey. Nearly all the IFRSs are undetected at a level of {approx}1 {mu}Jy in these new deep observations, and even the detections are consistent with confusion with unrelated galaxies. A stacked image implies that the median flux density is S{sub 3.6{mu}m} {approx} 0.2 {mu}Jy or less, giving extreme values of the radio-infrared flux density ratio. Comparison of these objects with known classes of object suggests that the majority are probably high-redshift radio-loud galaxies, possibly suffering from significant dust extinction.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1992

Design and structural analysis of Mars Rover RTG

The Mars Rover and Sample Return mission's radioisotope thermoelectric generator (RTG) is presently subjected to a structural and mass analysis in view of a reference mission scenario, an illustrative Rover design and Martian activities agenda, and RTG power system requirements and environmental constraints. The modular heat-source stack in the Rover RTG can be held together by axial load springs. The RTGs should be mounted on the Rover with a vertical orientation, in order to avoid the buildup of windborne Martian sand on its heat-rejection surfaces.

Schock, Alfred↗
NASA NTRSDate not supplied

Exploring the Jezero Crater Floor: Overview of Results from the Mars 2020 Perseverance Rover’s First Science Campaign

The Perseverance rover embarked on its first science campaign after landing in Jezero crater on February 18, 2021 and completing ~90 days of commissioning and Ingenuity helicopter activities. During this first campaign, Perseverance explored a large swath of Jezero’s crater floor, investigating and sampling several of the topographically lowest, and potentially oldest, rocks within the crater. Crater floor units: Perseverance explored the Máaz and Séítah formations (previously mapped as the Crater Floor Fractured Rough; Cf-fr and Crater Floor Fractured 1; Cf-f-1 units[1]). These are both widespread units in the crater that potentially correlate with units outside Jezero [2-4]. The Máaz fm. was distinguished from orbit by its mafic composition and densely cratered surface, and has various hypothesized origins, including lava flows[2] and volcaniclastic airfall [3]. The Máaz fm. is important for providing age/stratigraphic constraints on the Jezero western delta. If igneous, returned Máaz fm. samples may aid in calibrating the Mars crater chronology [2,5]and understanding Mars paleomagnetism and early igneous processes(see [6]). The Séítah fm. is olivine-bearing and has been interpreted to be related to a regional unit exposed along the inner rim of Jezero crater walls and occurs more broadly in the Nili Planum and Nili Fossae region. The olivine-bearing unit and its possible correlatives has a wide range of hypothesized origins including volcaniclastic airfall, impact melt, or aeolian and fluvial deposits [2-4,7,8]. The Séítahfm.is likely the oldest unit accessible to Perseverance and represents an important part of Jezero’s pre-delta-lacustrine history. As in the Máaz fm., the lithochemistry of the samples will help studies of early Mars igneous processes. The olivine-and carbonate-bearing components of this unit may also signify habitable conditions early in Jezero’s history, samples of which would be of high geochemical and astrobiological significance, as well as for understanding the martian carbon cycle(see [9]).

Mars 2020↗
DOE OSTI2018

Effect of Mn addition on deformation behaviour of 23% Cr low nickel duplex stainless steel

Highlights: • Increasing Mn content obviously affects dynamic softening behaviour of flow curves. • More complete austenite DRX occurred with middle Mn addition of 10.3% at 1 s{sup −1}. • The constitutive equations for different Mn addition alloys are developed. • The values of activation energy and Z parameter are lowest with middle Mn addition. • Different Mn addition processing maps with increasing strain were established. - Abstract: Isothermal compression testing of 23% Cr low nickel duplex stainless steels, with different Mn concentrations, was investigated in the temperature range of 1173–1423 K, the strain rate range of 0.01–10 s{sup −1} and with a height reduction of 70%. Increasing the Mn content from 6.3 to 14.1% affected the deformation dynamic softening behaviour of flow curves at lower temperature and higher strain rate. It was also observed that increasing the deformation stain rate contributed to flow softening, and was caused by dynamic recrystallization (DRX) as a function of Mn addition. Deformation microstructure analysis demonstrated that more complete austenite phase DRX occurred with 10.3% Mn addition than that with 6.3% Mn addition at 1 s{sup −1}, but an excessive Mn content of 14.1% was unfavourable due to the increase of austenite fraction and stacking fault energy enhancement. Increasing the strain rate to 10 s{sup −1} promoted austenite phase DRX at 1323 K with the Mn addition under large strain. Meanwhile, the ferrite phase DRX occurred at 1173 K/1–10 s{sup −1} with 6.3% Mn, and was weakened with higher Mn addition. Compared to the 6.3% and 14.1% Mn, continuous DRX occurred at 1323 K/1 s{sup −1} with 10.3% Mn, due to the larger fraction of high angle misorientations. The values for the activation energy and Zener–Hollomon parameter decreased with Mn addition from 6.3 to 10.3%, and then increased with a higher Mn addition of 14.1%, indicating that a proper content of Mn addition can reduce the thermal deformation resistance and promote DRX. The constitutive equations for different Mn addition alloys were developed using a hyperbolic sine equation. Processing maps with different Mn addition for the strains of 0.3, 0.6 and 1.2 were established. The 10.3% Mn content sample corresponded to the lowest instability region, implying that the workability was improved with the middle Mn addition.

36 MATERIALS SCIENCE↗
DOE OSTI2014

FeN foils by nitrogen ion-implantation

Iron nitride samples in foil shape (free standing, 500 nm in thickness) were prepared by a nitrogen ion-implantation method. To facilitate phase transformation, the samples were bonded on the substrate followed by a post-annealing step. By using two different substrates, single crystal Si and GaAs, structural and magnetic properties of iron nitride foil samples prepared with different nitrogen ion fluences were characterized. α″-Fe{sub 16}N{sub 2} phase in iron nitride foil samples was obtained and confirmed by the proposed approach. A hard magnetic property with coercivity up to 780 Oe was achieved for the FeN foil samples bonded on Si substrate. The feasibility of using nitrogen ion implantation techniques to prepare FeN foil samples up to 500 nm thickness with a stable martensitic phase under high ion fluences has been demonstrated. A possible mechanism was proposed to explain this result. This proposed method could potentially be an alternative route to prepare rare-earth-free FeN bulk magnets by stacking and pressing multiple free-standing thick α″-Fe{sub 16}N{sub 2} foils together.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2012

MEASURING THE GEOMETRY OF THE UNIVERSE FROM WEAK GRAVITATIONAL LENSING BEHIND GALAXY GROUPS IN THE HST COSMOS SURVEY

Gravitational lensing can provide pure geometric tests of the structure of spacetime, for instance by determining empirically the angular diameter distance-redshift relation. This geometric test has been demonstrated several times using massive clusters which produce a large lensing signal. In this case, matter at a single redshift dominates the lensing signal, so the analysis is straightforward. It is less clear how weaker signals from multiple sources at different redshifts can be stacked to demonstrate the geometric dependence. We introduce a simple measure of relative shear which for flat cosmologies separates the effect of lens and source positions into multiplicative terms, allowing signals from many different source-lens pairs to be combined. Applying this technique to a sample of groups and low-mass clusters in the COSMOS survey, we detect a clear variation of shear with distance behind the lens. This represents the first detection of the geometric effect using weak lensing by multiple, low-mass groups. The variation of distance with redshift is measured with sufficient precision to constrain the equation of state of the universe under the assumption of flatness, equivalent to a detection of a dark energy component {Omega}{sub X} at greater than 99% confidence for an equation-of-state parameter -2.5 {<=} w {<=} -0.1. For the case w = -1, we find a value for the cosmological constant density parameter {Omega}{sub {Lambda}} = 0.85{sup +0.044}{sub -}0{sub .19} (68% CL) and detect cosmic acceleration (q{sub 0} < 0) at the 98% CL. We consider the systematic uncertainties associated with this technique and discuss the prospects for applying it in forthcoming weak-lensing surveys.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Performance of the AstroPix Prototype Module for the Barrel Imaging Calorimeter at the ePIC Detector and in Space-Based Payloads

AstroPix is a high-voltage CMOS (HV-CMOS) monolithic active pixel sensor originally developed to enable precision gamma-ray imaging and spectroscopy in the medium-energy regime (~100 keV–100 MeV) based on the groundwork laid by ATLASpix and MuPix. It features a 500 μm pixel pitch, in-pixel amplification and digitization, and low power consumption (~3-4 mW/cm2), making it scalable for large-area, multilayer telescope detector planes. The detectors have a designed dynamic range of 25 keV to 700 keV. With these features, AstroPix meets the requirements of future space-based high-energy telescopes and the imaging layers of the Barrel Imaging Calorimeter (BIC) in the Electron-Proton/Ion Collider (ePIC) detector at the future Electron-Ion Collider (EIC). For the space-based payload, AstroPix is being integrated into sounding rocket and balloon payloads to demonstrate the technical readiness of the devices. For BIC, AstroPix-based imaging layers interleaved within the lead/scintillating-fiber (Pb/SciFi) sampling calorimeter provide granular shower imaging, enabling key performance features such as electron/pion or gamma/neutral pion separation. As part of the ongoing detector R&D efforts, we have been testing various AstroPix_v3 configurations: the single chip, a quad-chip assembly, a three-layer stack of quad chips, and a 9-chip module that represents the smallest prototype unit of the BIC imaging layer. This presentation will highlight recent performance test results from these AstroPix detector configurations.

Kim, Bobae (ORCID:0000000295396815)↗
DOE OSTI2023

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

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

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Blazars at the Cosmic Dawn

The uncharted territory of the high-redshift (z ≳ 3) universe holds the key to understanding the evolution of quasars. In an attempt to identify the most extreme members of the quasar population, that is, blazars, we have carried out a multiwavelength study of a large sample of radio-loud quasars beyond z = 3. Our sample consists of nine γ-ray-detected blazars and 133 candidate blazars selected based on the flatness of their soft X-ray spectra (0.3–10 keV photon index $\leqslant$ 1.75), including 15 with Nuclear Spectroscopic Telescope Array (NuSTAR) observations. The application of the likelihood profile stacking technique reveals that the high-redshift blazars are faint γ-ray emitters with steep spectra. The high-redshift blazars host massive black holes ($\langle$log M BH , M$\bigodot$ $\rangle$> 9) and luminous accretion disks ($\langle$L disk $\rangle$ > 10 46 erg s -1 ). Their broadband spectral energy distributions are found to be dominated by high-energy radiation, indicating their jets are among the most luminous ones. Focusing on the sources exhibiting resolved X-ray jets (as observed with the Chandra satellite), we find the bulk Lorentz factor to be larger with respect to other z > 3 blazars, indicating faster moving jets. In this paper, we conclude that the presented list of high-redshift blazars may act as a reservoir for follow-up observations, such as with NuSTAR, to understand the evolution of relativistic jets at the dawn of the universe.

79 ASTRONOMY AND ASTROPHYSICS↗