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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Green micromachining of ceramics using tungsten carbide micro-endmills

This paper presents an experimental analysis on micromachining of green-state silicon carbide (SiC) and aluminum nitride (AlN) using uncoated tungsten carbide (WC) micro-endmills. Although the unique properties of ceramics make them ideal materials for many applications involving micro-scale features, the industrial adaptation of ceramics at the micro-scale has been hindered due to the lack of viable ceramic micro-manufacturing techniques. Green micromachining (GMM), where micro-scale features are created by micromachining green-state ceramics that contain ceramic particles and a polymer binder, offers a potential solution for this problem by affording tremendous improvements in micromachinability with respect to sintered ceramics. After the completion of GMM, the green parts are debound and sintered to obtain the final component with the desired microscale features. In this work, we evaluated GMM characteristics of powder-injection molded green-state SiC and AlN to correlate process conditions and green-material compositions with the micromachining forces, quality, and tool wear. An experimental study that involves full immersion micromilling tests with 254 μm diameter micro-endmills at different cutting speeds and feed rates is conducted. For each of the two materials, two binder states (with and without wax) and two powder states (with micro particles only, or with both micro- and nanoparticles) are investigated. Green micromachining forces, specific energies and the resulting surface roughness are analyzed quantitatively. A qualitative analysis of burr formation and channel quality, as well as a preliminary study on micro-tool wear are also performed. Both the machining conditions and the material compositions are seen to have a strong effect on micro-machinability of green-state ceramics. Overall, we conclude that GMM can be a viable ceramic micro-manufacturing strategy if favorable (or optimal) micromachining and material parameters are identified through the presented (or a similar) micromachinability study.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Pair distribution function analysis of neutron-irradiated silicon carbide

We have employed x-ray total scattering to investigate the structure of polycrystalline 3C-silicon carbide following neutron irradiation. Here, the structure as a function of irradiation temperature and dose was quantified by analyzing pair distribution functions. Although the SiC matrix retains its crystal structure after irradiation, a significant increase in the diffuse scattering component is observable indicating that neutron irradiation leads to changes in both the short- and medium-range order. These changes include both an irradiation dose- and temperature-dependent increase in the vacancy concentration leading to an increase in the Si and C atomic displacement parameters. A dose-dependent decrease in the size of defect free material is also quantified from the structural refinements due to an increase in the number of defects and defect clusters. Evidence of additional correlations in the short-range order (up to ~4 Å) from differential pair distribution function analysis indicate that combinations of atomistic defects including anti-site defects, vacancies and defect clusters are present after these irradiation conditions. Such structural information will be valuable for direct comparison of experimental and simulated atomic structures of irradiated silicon carbide.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Uranium carbide properties for advanced fuel modeling – A review

Uranium carbides are receiving renewed interest as a preferred nuclear fuel composition for advanced reactors due to their numerous favorable properties. Like many other refractory and transition metal carbides these compounds exist in both hypo- and hyper-stoichiometric compositions which results in significant variations in physical, thermal, and mechanical properties. This manuscript surveys both historic and recent literature to compile important properties data mainly as a function of temperature and carbon content to support fuel performance modeling. Expressions and fits for such properties are also suggested when allowed by complete data sets. Finally, the manuscript also attempts to highlight gaps and discrepancies in the reported data to assist the nuclear fuels community identify key areas that may require further attention in terms of future research and development.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Degradation of a Cr-Mo steel by carbide precipitation over long-term service

Microstructure of the 40-year service-exposed 1Cr-0.5Mo steel extracted from pressure vessels through the boat sampling technique was characterized using x-ray diffraction, field-emission scanning electron microscopy, energy dispersive spectrometry, electron backscatter diffraction, focused ion beam, and transmission electron microscopy. The microstructure degradation during long-term service was identified. Statistical crystal plastic ity models were developed to correlate the microstructure and mechanical properties quantitatively. The steel is found significantly strengthened but slightly embrittled. Nanoscale Mo 2 C carbides have nucleated within the ferrite matrix over the long-term service, resulting in significant strengthening of the matrix. The coarser grain boundary Cr 23 C 6 carbides, on the other hand, act as the damage accumulation sites and lead to the degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Thin-Film Stabilization and Magnetism of η -Carbide-Type Iron Nitrides

Transition-metal nitrides in ..eta..-carbide-type structures exhibit unusual bonding motifs and proximity to magnetic instabilities. Yet they remain unexplored in thin-film form due to the difficulty of stabilizing nitrogen-poor ternaries among competing phases. Here, we report the thin-film synthesis and phase-stability mapping of the ..eta..-nitride systems Fe-W-N and Fe-Mo-N. Amorphous Fe-M-N (M = W, Mo) combinatorial libraries deposited by reactive cosputtering crystallize upon rapid thermal annealing, enabling systematic identification of synthesis windows as a function of composition and annealing temperature. Using laboratory powder X-ray diffraction and synchrotron grazing incidence wide-angle X-ray scattering, we establish that Fe 3 Mo 3 N-based ..eta..-carbide phases form over a substantially broader compositional and thermal range than W-based compositions, where ..eta.. structures are stabilized only when the films are Fe-rich. These trends are rationalized using mixed chemical-potential vs composition phase diagrams that capture the narrow nitrogen chemical-potential stability of ..eta..-nitrides. Magnetic measurements reveal that ferromagnetism is induced in Fe-rich Fe 3.54 Mo 2.46 N with a small exchange-bias-like response that is absent in Fe 3 W 3 N-based compositions, highlighting the sensitivity of magnetic behavior to modest deviations from stoichiometry. This work establishes practical thin-film synthesis routes for ..eta..-nitride materials and demonstrates how composition can be tuned to access emergent magnetic phenomena in these complex nitrides.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Guidelines for Synthesis and Processing of Two-Dimensional [2D] Titanium Carbide (Ti 3 C 2 T x MXene)

Two-dimensional (2D) transition metal carbides, carbonitrides, and nitrides (MXenes) were discovered in 2011. Since the original discovery, more than 20 different compositions have been synthesized by the selective etching of MAX phase and other precursors and many more theoretically predicted. They offer a variety of different properties, making the family promising candidates in a wide range of applications, such as energy storage, electromagnetic interference shielding, water purification, electrocatalysis, and medicine. These solution-processable materials have the potential to be highly scalable, deposited by spin, spray, or dip coating, painted or printed, or fabricated in a variety of ways. Due to this promise, the amount of research on MXenes has been increasing, and methods of synthesis and processing are expanding quickly. The fast evolution of the material can also be noticed in the wide range of synthesis and processing protocols that determine the yield of delamination, as well as the quality of the 2D flakes produced. Furthermore we describe the experimental methods and best practices we use to synthesize the most studied MXene, titanium carbide (Ti 3 C 2 T x ), using different etchants and delamination methods. We also explain effects of synthesis parameters on the size and quality of Ti 3 C 2 T x and suggest the optimal processes for the desired application.

36 MATERIALS SCIENCE↗
DOE OSTI2019

CO, CO 2 , and H 2 Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon and Metal Sites

A systematic study on the adsorption of atomic and molecular hydrogen and carbon oxides on cubic (001) and hexagonal (0001) WC surfaces by periodical density functional theory is reported. Calculations have been performed by employing the Perdew–Burke–Ernzerhof exchange correlation functional with van der Waals corrections to account for the dispersive force term. In addition, dipole corrections were applied for W- and C-terminated hexagonal WC(0001) surfaces. Good agreement is found between calculated and reported data for representative bulk properties. Regarding surface properties, our results indicate that atomic hydrogen adsorbs quite strongly while H 2 does, in general, dissociatively on the studied surfaces, with very small energy barriers (<0.35 eV) for the cleavage of the H–H bonds. The C sites of the carbide play an essential role in the binding of H atoms and the cleavage of H–H bonds. Studies examining the interaction of tungsten carbide with CO and CO 2 also evidence the importance of C sites. The reactivity of C- and W-terminated (0001) hexagonal WC surfaces significantly differs. Atomic hydrogen, carbon monoxide, and CO 2 are more stable on a C- than on a W-terminated surface, and only this latter termination is able to cleave spontaneously a C–O bond of the CO 2 molecule. This difference in reactivity may open a number of possibilities for fine-tuning the selectivity of the resulting material or designing compounds catalytically active for specific reactions by carefully adjusting the proportion of C, W, and mixed terminations during the synthesis procedure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Supported Molybdenum Carbide Nanoparticles as Hot Hydrogen Reservoirs for Catalytic Applications

Transition metal carbides have been long proposed as replacements for expensive Pt-group transition metals as heterogeneous catalysts for hydrogenation reactions, featuring similar to superior activities and selectivities. Combining experimental observations and theoretical calculations, we show that the hydrogenating capabilities of molybdenum carbide can be further improved by nanostructuring, as seen on MoC y nanoclusters anchored on an inert Au(111) support, revealing a more prominent role of Mo active sites in the easier H 2 adsorption, dissociation, H adatom diffusion, and elongated chemisorbed H 2 Kubas moieties formation when compared to the bulk δ-MoC(001) surface, thus explaining the observed stronger H 2 interaction and the larger formation of CH x species, making these systems ideal to catalyse hydrogenation reactions

36 MATERIALS SCIENCE↗
DOE OSTI2015

Nanostructured metal carbides for aprotic Li-O 2 batteries. New insights into interfacial reactions and cathode stability

The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O 2 to give lithium peroxide (Li 2 O 2 ), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li 2 O 2 oxidation on a passivated nanostructured metallic carbide (Mo 2 C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the Li x MoO 3 -passivated conductive interface formed on the carbide, owing to their close redox potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing Li x MoO 3 into the electrolyte, explaining the low charging potential.

25 ENERGY STORAGE↗
DOE OSTI2018

Roll-to-Roll Processing of Silicon Carbide Nanoparticle-Deposited Carbon Fiber for Multifunctional Composites

This work provides a proof of principle that a high volume, continuous throughput fiber coating process can be used to integrate semiconducting nanoparticles on carbon fiber surfaces to create multifunctional composites. By embedding silicon carbide nanoparticles in the fiber sizing, subsequent composite fabrication methods are used to create unidirectional fiber-reinforced composites with enhanced structural health monitoring (SHM) sensitivity and increased interlaminar strength. Additional investigations into the mechanical damping behavior of these functional composites reveal a significantly increased loss factor at the glass-transition temperature ranging from a 65 to 257% increase. Composites with both increased interlaminar strength and SHM sensitivity are produced from a variety of epoxy and silicon carbide nanoparticle concentrations. Overall, the best performing composite in terms of combined performance shows an increase of 47.5% in SHM sensitivity and 7.7% increase in interlaminar strength. Finally, this work demonstrates successful and efficient integration of nanoparticle synthesis into large-scale, structural applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Ordered Mesoporous Metal Carbides with Enhanced Anisole Hydrodeoxygenation Selectivity

Mesoporous metal carbides are of particular interest as catalysts for a variety of reactions because of their high surface areas, porous networks, nanosized walls, and unique electronic structures. In this work, two ordered mesoporous metal carbides, Mo 2 C and W 2 C, were synthesized using a nanocasting approach coupled with a simultaneous decomposition/carburization process under a continuous methane flow. The as-synthesized mesoporous Mo 2 C and W 2 C have three dimensionally ordered porous structures, large surface areas (70–90 m 2 g –1 ), and crystalline walls. In vapor-phase anisole hydrodeoxygenation (HDO) reactions, they exhibited turnover frequencies of approximately 9 and 2 × 10 –4 mol molCO –1 s –1 , respectively, at relatively low reaction temperatures (423–443 K) and ambient hydrogen pressures. Notably, the ordered mesoporous W 2 C catalyst showed a greater than 96% benzene selectivity in anisole HDO, the highest benzene selectivity reported to date.

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

Intrinsically Bifunctional and Tunable Tungsten Carbide Catalysts Enable Efficient PVC-Compatible Polyolefin Hydrocracking

Hydrocracking is a promising route for the chemical recycling of polyolefins (PO), converting them into short hydrocarbons over bifunctional catalysts with metal sites for hydrogenation and dehydrogenation, and Brønsted acid sites (BAS) for isomerization and C–C bond cleavage. However, PO feedstocks containing polyvinyl chloride (PVC) can release chlorine (Cl) under reaction conditions, deactivating conventional noble metal/zeolite catalysts. Moreover, the lack of site intimacy and the presence of micropores within conventional catalysts create challenges around the transport of high-molecular-weight, sterically encumbered polymer intermediates. Here, in this study, we report tungsten carbides (W x C) as a novel type of bifunctional catalysts that address these challenges. W/W 2 C phases on W x C offer “metal” sites, and −OH on WO x species introduces BAS in close proximity. The “metal”:BAS ratio can be tuned through carburization temperature, leading to a volcano-shaped activity trend reflecting the requirement for metal–BAS balance. Kinetic data demonstrate that each PO chain undergoes sequential cleavage, while trends in cracking ideality and selectivity follow those in short-alkane hydrocracking. On the per-BAS basis, W x C is more efficient than conventional bifunctional catalysts by more than an order of magnitude, due to enhanced polymer transport. They maintain or show increased activity with 10 wt % PVC in the substrate. This work establishes transition-metal carbides as earth-abundant bifunctional catalysts with unique site proximity and heteroatom compatibility. These features, along with the broad structure space for rational tuning, make them promising options to tackle specific challenges that polymer feedstocks present in hydrocracking.

Nwachukwu, Uchenna C. [Univ. of Akron, OH (United ↗
DOE OSTI2013

A Screened Hybrid DFT Study of Actinide Oxides, Nitrides, and Carbides

A systematic study of the structural, electronic, and magnetic properties of actinide oxides, nitrides, and carbides (AnX1–2 with X = C, N, O) is performed using the Heyd–Scuseria–Ernzerhof (HSE) hybrid functional. Our computed results show that the screened hybrid HSE functional gives a good description of the electronic and structural properties of actinide dioxides (strongly correlated insulators) when compared with available experimental data. However, there are still some problems reproducing the electronic properties of actinide nitrides and carbides (strongly correlated metals). In addition, in order to compare with the results by HSE, the structures, electronic, and magnetic properties of these actinide compounds are also investigated in the PBE and PBE+U approximation. Interestingly, the density of states of UN obtained with PBE compares well with the experimental photoemission spectra, in contrast to the hybrid approximation. This is presumably related to the need of additional screening in the Hartree–Fock exchange term of the metallic phases.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

A diuranium carbide cluster stabilized inside a C 80 fullerene cage

Unsupported non-bridged uranium–carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing I h (7)-C 80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@I h (7)-C 80 . This endohedral fullerene was prepared utilizing the Krätschmer–Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (Ni II -OEP) to produce UCU@I h (7)-C 80 ·[Ni II -OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium–carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@I h (7)-C 80 and the covalent nature of the U(f 1 )=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction

An overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO 2 RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO 2 RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH 4 ) current density of -421.63 mA/cm 2 and a CH 4 faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W 2 C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO 2 to produce CH 4 in a 700-h process under one sun illumination with a CO 2 RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO 2 and cleavage of the C-O bond—the most energy consuming elementary steps in other catalysts such as copper—become nearly spontaneous at the W2C surface. This results in instantaneous formation of adsorbed CO—an important reaction intermediate—and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Structure and density of silicon carbide to 1.5 TPa and implications for extrasolar planets

There has been considerable recent interest in the high-pressure behavior of silicon carbide, a potential major constituent of carbon-rich exoplanets. In this work, the atomic-level structure of SiC was determined through in situ X-ray diffraction under laser-driven ramp compression up to 1.5 TPa; stresses more than seven times greater than previous static and shock data. Here we show that the B1-type structure persists over this stress range and we have constrained its equation of state (EOS). Using this data we have determined the first experimentally based mass-radius curves for a hypothetical pure SiC planet. Interior structure models are constructed for planets consisting of a SiC-rich mantle and iron-rich core. Carbide planets are found to be ~10% less dense than corresponding terrestrial planets.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

An investigation of the long-range and local structure of sub-stoichiometric zirconium carbide sintered at different temperatures

ZrC 1-x (sub-stoichiometric zirconium carbide), a group IV transition metal carbide, is being considered for various high temperature applications. Departure from stoichiometry changes the thermo-physical response of the material. Reported thermo-physical properties exhibit, in some cases, a degree of scatter with one likely contributor to this being the uncertainty in the C/Zr ratio of the samples produced. Conventional, methods for assigning C/Zr to samples are determined either by nominal stochiometric ratios or combustion carbon analysis. In this study, a range of stoichiometries of hot-pressed ZrC 1-x were examined by SEM, XRD, Raman spectroscopy and static 13 C NMR spectroscopy and used as a basis to correct the C/Zr. Graphite, amorphous, and ZrC 1-x carbon signatures are observed in the 13 C NMR spectra of samples and are determined to vary in intensity with sintering temperature and stoichiometry. In this study a method is outlined to quantify the stoichiometry of ZrC 1-x and free carbon phases, providing an improvement over the sole use and reliance of widely adopted bulk carbon combustion analysis. We report significantly lower C/Zr values determined by 13 C NMR analysis compared with carbon analyser and nominal methods. Furthermore, the location of carbon disassociated from the ZrC 1-x structure is analysed using SEM and Raman spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Towards a mechanistic understanding of the sol–gel syntheses of ternary carbides

Sol–gel chemistry, while being extremely established, is to this day not fully understood, and much of the underlying chemistry and mechanisms are yet to be unraveled. Here, in this work, we elaborate on the sol–gel chemistry of Cr 2 GaC, the first layered ternary carbide belonging to the MAX phase family to ever be synthesized using this wet chemical approach. Leveraging a variety of both in- and ex situ characterization techniques, including X-ray and neutron powder diffraction, X-ray absorption fine structure analyses, total scattering analyses, and differential scanning calorimetry coupled with mass spectrometry, in-depth analyses of the local structures and reaction pathways are elucidated. While the metals first form tetrahedrally and octahedrally coordinated oxidic structures, that subsequently grow and crystallize into oxides, the carbon source citric acid sits on a separate reaction pathway, that does not merge with the metals until the very end. In fact, after decomposing it remains nanostructured and disordered graphite until the temperature allows for the reduction of the metal oxides into the layered carbide. Based on this, we hypothesize that the method is mostly applicable to systems where the needed metals are reducible by graphite around the formation temperature of the target phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗