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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Synthesis of Titanium Oxycarbide from Titanium Slag by Methane-Containing Gas

In this study, reaction steps of a process for synthesis of titanium oxycarbide from titanium slag were demonstrated. This process involves the reduction of titanium slag by a methane-hydrogen-argon mixture at 1473 K (1200 °C) and the leaching of the reduced products by hydrofluoric acid near room temperature to remove the main impurity (Fe{sub 3}Si). Some iron was formed by disproportionation of the main M{sub 3}O{sub 5} phase before gaseous reduction started. Upon reduction, more iron formed first, followed by reduction of titanium dioxide to suboxides and eventually oxycarbide.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Thermodynamic Stability of Molybdenum Oxycarbides Formed from Orthorhombic Mo 2 C in Oxygen-Rich Environments

Molybdenum carbide (Mo 2 C) nanoparticles and thin films are particularly suitable catalysts for catalytic fast pyrolysis (CFP) as they are effective for deoxygenation and can catalyze certain reactions that typically occur on noble metals. Oxygen deposited during deoxygenation reactions may alter the carbide structure, leading to the formation of oxycarbides, which can determine changes in catalytic activity or selectivity. Despite emerging spectroscopic evidence of bulk oxycarbides, so far there have been no reports of their precise atomic structure or their relative stability with respect to orthorhombic Mo 2 C. This knowledge is essential for assessing the catalytic properties of molybdenum (oxy)carbides for CFP. In this article, we use density functional theory (DFT) calculations to (a) describe the thermodynamic stability of surface and subsurface configurations of oxygen and carbon atoms for a commonly studied Mo-terminated surface of orthorhombic Mo 2 C and (b) determine atomic structures for oxycarbides with a Mo:C ratio of 2:1. The surface calculations suggest that oxygen atoms are not stable under the top Mo layer of the Mo 2 C(100) surface. Coupling DFT calculations with a polymorph sampling method, we determine (Mo 2 C) x O y oxycarbide structures for a wide range of oxygen compositions. Oxycarbides with lower oxygen content (y/x = 2) adopt layered structures reminiscent of the parent carbide phase, with flat Mo layers separated by layers of oxygen and carbon; for higher oxygen content, our results suggest the formation of amorphous phases, as the atomic layers lose their planarity with increasing oxygen content. We characterize the oxidation states of Mo in the oxycarbide structures determined computationally, and simulate their X-ray diffraction (XRD) patterns in order to facilitate comparisons with experiments. Our study may provide a platform for large-scale investigations of the catalytic properties of oxycarbides and their surfaces and for tailoring the catalytic properties for different desired reactions.

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

Zirconium Oxycarbide: A Highly Stable Catalyst Material for Electrochemical Energy Conversion

Abstract Metal carbides and oxycarbides have recently gained considerable interest due to their (electro)catalytic properties that differ from those of transition metals and that have potential to outperform them as well. The stability of zirconium oxycarbide nanopowders (ZrO 0.31 C 0.69 ), synthesized via a hybrid solid‐liquid route, is investigated in different gas atmospheres from room temperature to 800 °C by using in‐situ X‐ray diffraction and in‐situ electrical impedance spectroscopy. To feature the properties of a structurally stable Zr oxycarbide with high oxygen content, a stoichiometry of ZrO 0.31 C 0.69 has been selected. ZrO 0.31 C 0.69 is stable in reducing gases with only minor amounts of tetragonal ZrO 2 being formed at high temperatures, whereas it decomposes in CO 2 and O 2 gas atmosphere. From online differential electrochemical mass spectrometry measurements, the hydrogen evolution reaction (HER) onset potential is determined at −0.4 V RHE . CO 2 formation is detected at potentials as positive as 1.9 V RHE as ZrO 0.31 C 0.69 decomposition product, and oxygen is anodically formed at 2.5 V RHE , which shows the high electrochemical stability of this material in acidic electrolyte. This peopwery makes the material suited for electrocatalytic reactions at anodic potentials, such as CO and alcohol oxidation reactions, in general.

Chemistry↗
NASA NTRS1997

Tailoring Silicon Oxycarbide Glasses for Oxidative Stability

Blackglas(Trademark) polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using Si-29 nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.

Hurwitz, F. I.↗
DOE OSTI2025

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel Jana Howard1,3, Guang Yang3, Haiyan Zhao1*, Patrick Warren4, Tiankai Yao3, Steven Cavazos4 Elizabeth Sooby Wood4*, Ching-heng Shiau2 1 University of Idaho, Environmental Science, Idaho Falls, Idaho, USA 2 Boise State University, Microscopy and Characterization Suite, Idaho Falls, Idaho, USA 3 Idaho National Laboratory, Idaho Falls, Idaho, USA 4 University of Texas San Antonio, Department of Physics and Astronomy, San Antonio, Texas, USA *Corresponding author: haiyanz@uidaho.edu; elizabeth.soobywood@utsa.edu Tri-structural Isotropic (TRISO) particle fuel is the preferred choice for the newest and next-generation high-temperature nuclear reactors due to its robust construction [1]. The fuel design effectively contains fission products inside the particle at extremely high temperatures [2]. However, the effect of transition metal fission products on fuel performance and structural integrity remains largely unknown, creating uncertainties in predicting fuel performance and potential failure mechanisms [2]. For example, palladium (Pd) has a strong tendency to form intermetallic phases with uranium (U). These new phases tend to be hard and brittle which could lead to fracture of fuel kernel during irradiation [3,4]. Pd is not normally produced in high concentrations in normal fission reactions however, driving the production of Pd into the locality of a Uranium Oxycarbide (UCO) nuclear fuel provides an opportunity to closely observe the diffusion and chemical interactions. This study focuses on detailed transmission electron microscopy characterization of the intermetallic phases formed by the interaction between a UCO kernel and a Pd bar after annealing at 1100 °C for 100 hours. Figure 1 provides an overview of the UCO kernel in contact with the Pd bar. The UCO-Pd sample surface was examined using a Focused Ion Beam (FIB) Quanta 3D FEG FEI in VCD detector mode at 10kV, 83pA to reveal surface features. Several key surface features in the interaction region were observed including: (1) a small area with dendritic microstructure, (2) color contrast near the UCO kernel and Pd boundary, and (3) darker and lighter regions throughout the sample surface. To analyze diffusion behavior, FIB was used to prepare lamellae from five different areas of the UCO-Pd sample, as well as one for the as-received sample. These lamellae were examined using a Scanning Transmission Electron Microscope ThermoFisher Spectra 300 (STEM-Spectra). Energy Dispersive Spectroscopy results confirmed the diffusion between the UCO fuel and Pd bar. Figure 2 shows the identified phases of UC, UO2, and Pd dispersed throughout the interaction region. It was also found that the Pd concentration decreases as the radial distance from the UCO-Pd interface increases. The Pd concentration was 36.93% atomic fraction 11µm from the interaction region then decreased to 7.51% atomic fraction at 257 µm away from the interaction region. Figure 3 shows how concentrations of U and Pd vary across the interaction zone, highlighting the extent of diffusion. This study confirms that Pd interacts with surrounding material to form U-Pd phase and diffusion zones. These diffusion zones vary in composition depending on its radial distance from the point of contact with the Pd bar. These findings contribute to a deeper understanding of the fission product behavior in high temperature nuclear fuels, aiding in the prediction and mitigation of potential fuel degradation mechanisms. A B C Fig. 1. SEM micrographs of UCO fuel kernel in contact with solid Pd bar and the lift out locations. Figure 1A shows UCO fuel kernel in contact with solid Pd bar. Figure 1B shows a higher magnification image of the UCO fuel-Pd interaction zone. Figure 1C shows lift out sites for the lamellae. A B C Fig 2. EDS maps reveal the distribution of U, O, and Pd in location 3. Figure 2A shows the distribution of uranium. Figure 2B shows the distribution of oxygen. Figure 2C shows the distribution of palladium. A B C Fig 3. Palladium and uranium concentration across interaction zone in location 2. Figure 3A shows EDS map of lift out number 2. Figure 3B shows a zoomed in EDS map taken from the interaction zone. Figure 3C shows a line graph of uranium and palladium concentrations across the interaction zone. References: 1. B.E. Wells, N.R. Phillips, K.J. Geelhood. Pacific West Laboratory. (2021). TRISO Fuel: Properties and Failure Modes. https://www.nrc.gov/docs/ML2117/ML21175A152.pdf (Accessed January 16, 2025). 2. American Nuclear Society. TRISO Fuel Development Progresses in INL, ORNL. https://www.gen-4.org/gif/upload/docs/application/pdf/2014-03/nov13nn_fuel_reprint.pdf (Accessed January 16, 2025) 3. Clark R.A., M.A. Con

36 - MATERIALS SCIENCE↗
DOE OSTI2025

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel Jana Howard1,3, Guang Yang3, Haiyan Zhao1*, Patrick Warren4, Tiankai Yao3, Steven Cavazos4 Elizabeth Sooby Wood4*, Ching-heng Shiau2 1 University of Idaho, Environmental Science, Idaho Falls, Idaho, USA 2 Boise State University, Microscopy and Characterization Suite, Idaho Falls, Idaho, USA 3 Idaho National Laboratory, Idaho Falls, Idaho, USA 4 University of Texas San Antonio, Department of Physics and Astronomy, San Antonio, Texas, USA *Corresponding author: haiyanz@uidaho.edu; elizabeth.soobywood@utsa.edu Tri-structural Isotropic (TRISO) particle fuel is the preferred choice for the newest and next-generation high-temperature nuclear reactors due to its robust construction [1]. The fuel design effectively contains fission products inside the particle at extremely high temperatures [2]. However, the effect of transition metal fission products on fuel performance and structural integrity remains largely unknown, creating uncertainties in predicting fuel performance and potential failure mechanisms [2]. For example, palladium (Pd) has a strong tendency to form intermetallic phases with uranium (U). These new phases tend to be hard and brittle which could lead to fracture of fuel kernel during irradiation [3,4]. Pd is not normally produced in high concentrations in normal fission reactions however, driving the production of Pd into the locality of a Uranium Oxycarbide (UCO) nuclear fuel provides an opportunity to closely observe the diffusion and chemical interactions. This study focuses on detailed transmission electron microscopy characterization of the intermetallic phases formed by the interaction between a UCO kernel and a Pd bar after annealing at 1100 °C for 100 hours. Figure 1 provides an overview of the UCO kernel in contact with the Pd bar. The UCO-Pd sample surface was examined using a Focused Ion Beam (FIB) Quanta 3D FEG FEI in VCD detector mode at 10kV, 83pA to reveal surface features. Several key surface features in the interaction region were observed including: (1) a small area with dendritic microstructure, (2) color contrast near the UCO kernel and Pd boundary, and (3) darker and lighter regions throughout the sample surface. To analyze diffusion behavior, FIB was used to prepare lamellae from five different areas of the UCO-Pd sample, as well as one for the as-received sample. These lamellae were examined using a Scanning Transmission Electron Microscope ThermoFisher Spectra 300 (STEM-Spectra). Energy Dispersive Spectroscopy results confirmed the diffusion between the UCO fuel and Pd bar. Figure 2 shows the identified phases of UC, UO2, and Pd dispersed throughout the interaction region. It was also found that the Pd concentration decreases as the radial distance from the UCO-Pd interface increases. The Pd concentration was 36.93% atomic fraction 11µm from the interaction region then decreased to 7.51% atomic fraction at 257 µm away from the interaction region. Figure 3 shows how concentrations of U and Pd vary across the interaction zone, highlighting the extent of diffusion. This study confirms that Pd interacts with surrounding material to form U-Pd phase and diffusion zones. These diffusion zones vary in composition depending on its radial distance from the point of contact with the Pd bar. These findings contribute to a deeper understanding of the fission product behavior in high temperature nuclear fuels, aiding in the prediction and mitigation of potential fuel degradation mechanisms. A B C Fig. 1. SEM micrographs of UCO fuel kernel in contact with solid Pd bar and the lift out locations. Figure 1A shows UCO fuel kernel in contact with solid Pd bar. Figure 1B shows a higher magnification image of the UCO fuel-Pd interaction zone. Figure 1C shows lift out sites for the lamellae. A B C Fig 2. EDS maps reveal the distribution of U, O, and Pd in location 3. Figure 2A shows the distribution of uranium. Figure 2B shows the distribution of oxygen. Figure 2C shows the distribution of palladium. A B C Fig 3. Palladium and uranium concentration across interaction zone in location 2. Figure 3A shows EDS map of lift out number 2. Figure 3B shows a zoomed in EDS map taken from the interaction zone. Figure 3C shows a line graph of uranium and palladium concentrations across the interaction zone. References: 1. B.E. Wells, N.R. Phillips, K.J. Geelhood. Pacific West Laboratory. (2021). TRISO Fuel: Properties and Failure Modes. https://www.nrc.gov/docs/ML2117/ML21175A152.pdf (Accessed January 16, 2025). 2. American Nuclear Society. TRISO Fuel Development Progresses in INL, ORNL. https://www.gen-4.org/gif/upload/docs/application/pdf/2014-03/nov13nn_fuel_reprint.pdf (Accessed January 16, 2025) 3. Clark R.A., M.A. Con

36 - MATERIALS SCIENCE↗
DOE OSTI2019

Reactive Force Field for Simulations of the Pyrolysis of Polysiloxanes into Silicon Oxycarbide Ceramics

We provide a new reactive force field (ReaxFF) for simulations of silicon oxycarbide (SiCO) ceramics and of their syntheses from inorganic polymer precursors. The validity of the force field is extensively tested against experimental and computational thermochemical data. Its performance in simulation at elevated temperatures is gauged by the results of comprehensive ab initio molecular dynamics simulations. We apply the force field to the formation of amorphous SiCO in a simulated polymer pyrolysis. Modeling results are in good agreement with experimental observations and allow new insights into the formation of graphene segregations embedded in an amorphous oxycarbide matrix. The new ReaxFF for Si-C-O-H compounds enables large- scale and long-time atomistic simulations with unprecedented fidelity.

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

Equilibrium of [Si]/(SiO{sub 2}) in Carbothermic Selective Reduction of Titanium Concentrate Ore for the Preparation of Titanium Oxycarbide

Carbothermic selective reduction of titanium concentrate ore for the preparation of titanium oxycarbide was presented and SiO{sub 2} was found to be partly reduced during the process. The equilibrium relationship between Si dissolved in metallic Fe and SiO{sub 2} existed in corresponding slag was analyzed thermodynamically, and then revealed by a series of designed equilibration experiments. The results are in accordance with the calculated values obtained from thermodynamic analysis and have well explained the phenomenon that part of SiO{sub 2} is reduced during selective reduction processing of titanium concentrate ore.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Hydrogen enhances the radiation resistance of amorphous silicon oxycarbides

Here, we use first principles molecular dynamics to investigate unit displacement processes in amorphoussilicon oxycarbides (SiOC) and demonstrate that the introduction of hydrogen (H) into these materialsenhances their radiation resistance. Our simulations show that 100 eV knock-ons in H-free SiOC redistribute C through the formation of CeO and CeC bonds. H counteracts this trend by passivating dangling O bonds and preventing C from coming out of solution. This effect arises from the exceptionally high mobility of H, which leads to the saturation of radiation-induced O and C radicals even before the thermal-spike induced by a high-energy knock-on dies down. Our work suggests that fully hydrogenated SiOC is a promising radiation-resistant material for future nuclear energy applications.

08 HYDROGEN↗
DOE OSTI2012

FABRICATION OF URANIUM OXYCARBIDE KERNELS AND COMPACTS FOR HTR FUEL

As part of the program to demonstrate tristructural isotropic (TRISO)-coated fuel for the Next Generation Nuclear Plant (NGNP), Advanced Gas Reactor (AGR) fuel is being irradiation tested in the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL). This testing has led to improved kernel fabrication techniques, the formation of TRISO fuel particles, and upgrades to the overcoating, compaction, and heat treatment processes. Combined, these improvements provide a fuel manufacturing process that meets the stringent requirements associated with testing in the AGR experimentation program. Researchers at Idaho National Laboratory (INL) are working in conjunction with a team from Babcock and Wilcox (B&W) and Oak Ridge National Laboratory (ORNL) to (a) improve the quality of uranium oxycarbide (UCO) fuel kernels, (b) deposit TRISO layers to produce a fuel that meets or exceeds the standard developed by German researches in the 1980s, and (c) develop a process to overcoat TRISO particles with the same matrix material, but applies it with water using equipment previously and successfully employed in the pharmaceutical industry. A primary goal of this work is to simplify the process, making it more robust and repeatable while relying less on operator technique than prior overcoating efforts. A secondary goal is to improve first-pass yields to greater than 95% through the use of established technology and equipment. In the first test, called “AGR-1,” graphite compacts containing approximately 300,000 coated particles were irradiated from December 2006 to November 2009. The AGR-1 fuel was designed to closely replicate many of the properties of German TRISO-coated particles, thought to be important for good fuel performance. No release of gaseous fission product, indicative of particle coating failure, was detected in the nearly 3-year irradiation to a peak burn up of 19.6% at a time-average temperature of 1038–1121°C. Before fabricating AGR-2 fuel, each fabrication process was improved and changed. Changes to the kernel fabrication process included replacing the carbon black powder feed with a surface-modified carbon slurry and shortening the sintering schedule. AGR-2 TRISO particles were produced in a 6-inch diameter coater using a charge size about 21-times that of the 2-inch diameter coater used to coat AGR-1 particles. The compacting process was changed to increase matrix density and throughput by increasing the temperature and pressure of pressing and using a different type of press. AGR-2 fuel began irradiation in the ATR in late spring 2010.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Helium Irradiation and Implantation Effects on the Structure of Amorphous Silicon Oxycarbide

Despite recent interest in amorphous ceramics for a variety of nuclear applications, many details of their structure before and after irradiation/implantation remain unknown. Here we investigated the short-range order of amorphous silicon oxycarbide (SiOC) alloys by using the atomic pair-distribution function (PDF) obtained from electron diffraction. The PDF results show that the structure of SiOC alloys are nearly unchanged after both irradiation up to 30 dpa and He implantation up to 113 at%. TEM characterization shows no sign of crystallization, He bubble or void formation, or segregation in all irradiated samples. Irradiation results in a decreased number of Si-O bonds and an increased number of Si-C and C-O bonds. This study sheds light on the design of radiation-tolerant materials that do not experience helium swelling for advanced nuclear reactor applications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Rapid and damage-free outgassing of implanted helium from amorphous silicon oxycarbide

Damage caused by implanted helium (He) is a major concern for material performance in future nuclear reactors. We use a combination of experiments and modeling to demonstrate that amorphous silicon oxycarbide (SiOC) is immune to He-induced damage. By contrast with other solids, where implanted He becomes immobilized in nanometer-scale precipitates, He in SiOC remains in solution and outgasses from the material via atomic-scale diffusion without damaging its free surfaces. However, the behavior of He in SiOC is not sensitive to the exact concentration of carbon and hydrogen in this material, indicating that the composition of SiOC may be tuned to optimize other properties without compromising resistance to implanted He.

42 ENGINEERING↗
DOE OSTI2015

Hydrogen reverses the clustering tendency of carbon in amorphous silicon oxycarbide

Amorphous silicon oxycarbide (SiOC) is of great technological interest. However, its atomic-level structure is not well understood. Using density functional theory calculations, we show that the clustering tendency of C atoms in SiOC is extremely sensitive to hydrogen (H): without H, the C-C interaction is attractive, leading to enrichment of aggregated SiC 4 tetrahedral units; with hydrogen, the C-C interaction is repulsive, leading to enrichment of randomly distributed SiCO 3 tetrahedral units. Our results suggest that conflicting experimental characterizations of C distributions may be due to differing amounts of H present in the samples investigated. Our work also opens a path for tailoring the properties of SiOC by using the total H content to control the C distribution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The origin of white luminescence from silicon oxycarbide thin films

Silicon oxycarbide (SiC{sub x}O{sub y}) is a promising material for achieving strong room-temperature white luminescence. The present work investigated the mechanisms for light emission in the visible/ultraviolet range (1.5–4.0 eV) from chemical vapor deposited amorphous SiC{sub x}O{sub y} thin films, using a combination of optical characterizations and electron paramagnetic resonance (EPR) measurements. Photoluminescence (PL) and EPR studies of samples, with and without post-deposition passivation in an oxygen and forming gas (H{sub 2} 5 at. % and N{sub 2} 95 at. %) ambient, ruled out typical structural defects in oxides, e.g., Si-related neutral oxygen vacancies or non-bridging oxygen hole centers, as the dominant mechanism for white luminescence from SiC{sub x}O{sub y}. The observed intense white luminescence (red, green, and blue emission) is believed to arise from the generation of photo-carriers by optical absorption through C-Si-O related electronic transitions, and the recombination of such carriers between bands and/or at band tail states. This assertion is based on the realization that the PL intensity dramatically increased at an excitation energy coinciding with the E{sub 04} band gaps of the material, as well as by the observed correlation between the Si-O-C bond density and the PL intensity. An additional mechanism for the existence of a blue component of the white emission is also discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2012

Carbothermal synthesis of titanium oxycarbide as electrocatalyst support with high oxygen evolution reaction activity

Carbothermal reduction of semiconducting TiO2 into highly conductive titanium oxycarbide (TiOxCy) was investigated. The thermally produced uniform carbon layer on TiO2 (Degussa P25) protects the TiO2 nanoparticles from sintering and, at the same time, supplies the carbon source for doping TiO2 with carbon. At low temperatures (e. g., 700 degrees C), carbon only substitutes part of the oxide and distorts the TiO2 lattice to form TiO2-xCx with only substitutional carbon. When the carbon-doped TiO2 is annealed at a higher temperature (1100 degrees C), x-ray diffraction and x-ray photoelectron spectroscopy results showed that TiOxCy, a solid solution of TiO and TiC, was formed, which displays different diffraction peaks and binding energies. It was shown that TiOxCy has much better oxygen revolution reaction activity than TiO2 or TiO2-xCx. Further studies showed that the TiOxCy obtained can be used as a support for metal electrocatalyst, leading to a bifunctional catalyst effective for both oxygen reduction and evolution reactions.

Huang, K↗