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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Zero Valent Iron for Reductive Removal of Technetium-99 from Aqueous Sulfate Solutions - 20347

This research investigates the reductive removal of technetium-99 ({sup 99}Tc) by zero valent iron (ZVI) from low activity waste (LAW) off-gas condensate simulant as a secondary treatment after recovery from vitrification planned at the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Due to its high volatility, only a fraction of Tc{sup (VII)} will be incorporated into glass waste forms. Volatilized Tc will be captured by an off-gas treatment system with current plans to recycle off-gas condensate back to the vitrification facility. The scheme with off-gas recycling will increase Tc loading in the glass waste, but will also increase the concentrations of sulfate, halides, and other problematic constituents impeding overall LAW processing and increasing volume of the glass product. This study focuses on Tc{sup (VII)} removal by ZVI as a feasible pathway to minimize off-gas condensate recycling, which may result in a reduction in the volumes of LAW waste to be immobilized and subsequent cost savings. ZVI is an established treatment agent for redox-active contaminants such as trichloroethylene, nitrate, arsenic, chromium, phenol, and others. It is a commercially available and cost-effective material. Our previous experiments showed that ZVI is very efficient for the reductive removal of {sup 99}Tc. In this work we studied ZVI oxidation under aerobic conditions at pH 7 with 0.1 M Na{sub 2}SO{sub 4} solution (ionic strength, IS, 0.3 M) in the presence and absence of {sup 99}Tc. The concentration of {sup 99}Tc and the changes in pH, dissolved oxygen (DO), and oxidation-reduction potential (ORP) of the simulated solutions were monitored over 8 days. The formation of iron oxide phases was probed by X-ray diffraction (XRD). Obtained results suggest that ZVI contact time with {sup 99}Tc containing solutions for 6 hours resulted in nearly complete removal of {sup 99}Tc from the aqueous phase. XRD analysis showed that the oxidation of ZVI is rapid with formation of magnetite (Fe{sub 3}O{sub 4}) with minor percentage of goethite and maghemite. This work is a part of a larger set of studies investigating the feasibility of {sup 99}Tc reductive removal from the LAW off-gas condensate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

FY17 end of year MARMOT materials model development update

This document summarizes the lower length scale progress made in FY17 in developing materials models for fuel performance modeling of oxide fuels and their implementation in the MARMOT code. The progress covers the development of a phase field recrystallization model for high-burnup structure formation in oxide fuels, a phase field model for studying stage-3 fission gas release in UO 2 , a phase-field model for irradiation-enhanced densification in UO 2 , a quantitative model for hydride morphology in Zirconium based cladding, and the calculation of hydrogen diffusivity under stress in various Zirconium based alloys as cladding candidates. Further development in the MARMOT code has been carried out as well to improve the multi-phase, multi-component phase field model, the representation of interfacial energy in the Kim-Kim-Suzuki model, and the description of interfacial stress. For most of the above, separated reports have been generated with detailed description. Here a brief summary is provided, with references pointing to the detailed reports to guide interested readers.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Effects of mechanically alloying Al 2 O 3 and Y 2 O 3 additives on the liquid phase sintering behavior and properties of SiC

In order to improve the sintering of SiC, mixtures of Al 2 O 3 and Y 2 O 3 powders are commonly included as sintering additives. The aim of this work was to use mechanically alloyed Al 2 O 3 –Y 2 O 3 mixtures as sintering additives to promote liquid phase sintering of SiC using spark plasma sintering. The results showed that milling reduced the particle size of the powders and led to the formation of complex oxide phases (YAP, YAM, and YAG) at low temperatures. As the ball milling time increased, the mass loss of specimens sintered with mechanically alloyed Al 2 O 3 –Y 2 O 3 mixtures decreased, and accordingly the relative density increased. However, the hardness and flexural strength of sintered SiC specimens first increased and then decreased. Because the specimens prepared with oxides milled for a long time contained too much YAG/YAP and accordingly too much liquid at sintering temperature. This negatively affected the mechanical properties of the SiC specimens because of the increased volume of the complex oxide phases, which have inferior mechanical properties to SiC, in the sintered specimens. In conclusion, when the ball milling time was 6h, the hardness (24.02 GPa) and flexural strength (655.61 MPa) of the SiC specimens reached maximum values.

36 MATERIALS SCIENCE↗
DOE OSTI2017

New Oxide Materials for an Ultra High Temperature Environment

In this project, a new oxide material, Hf 6 Ta 2 O 17 has been successfully synthesized by the controlled oxidization of Hf-Ta alloys. This oxide exhibits good oxidation resistance, high temperature phase stability up to more than 2000°C, low thermal conductivity and thus could serve as a component or a coating material in an ultrahigh temperature environment. We have examined the microstructure evolution and phase formation sequence during the oxidation exposure of Hf-Ta alloys at 1500°C and identified that the oxidation of a Hf-26.7atomic %Ta alloy leads to the formation of a single phase adherent Hf 6 Ta 2 O 17 with a complex atomic structure i.e. superstructure. The overall reactive diffusion pathway is consistent with the calculated Hf-Ta-O ternary phase diagram. Besides the synthesis of Hf 6 Ta 2 O 17 superstructure by oxidizing Hf-Ta alloys, we have also developed a synthesis method based upon the reactive sintering of the correct ratios of mixed powders of HfO 2 and Ta 2 O 5 and verified the low thermal conductivity of Hf 6 Ta 2 O 17 superstructure on these samples. We have completed a preliminary analysis of the oxidation kinetics for Hf 6 Ta 2 O 17 , which shows an initial parabolic oxidation kinetics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Accelerated and heterogeneous corrosion of Cr-doped uranium nitride fuel pellets

The steam oxidation of Cr-doped UN fuel pellets is analyzed during sequential isothermal holds up to 720 °C. In situ neutron diffraction results show how Cr is accommodated in a secondary U 2 CrN 3 phase, leading to the formation of a duplex UN/U 2 CrN 3 microstructure. Under corrosion, the oxidation of the two phases begins at 400 °C for UN and 430 °C for U 2 CrN 3 , respectively. Because the UN phase is preferentially oxidized in the presence of U 2 CrN 3 , addition of Cr in UN based nuclear fuel is found to accelerate the corrosion rate. At 430 °C the oxidation of UN in the UN/U 2 CrN 3 microstructure is ~ 5 times faster than pure UN, increasing to ~19 times faster at 460 °C. The oxidation of U 2 CrN 3 produces UO 2 via the formation of two transient intermediate phases. In situ neutron diffraction enables oxidation processes of UN and U 2 CrN 3 components to be followed separately within the two-phase system.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Optical spectroscopy and modeling of uranium gas-phase oxidation: Progress and perspectives

We report that studies related to U gas-phase oxidation through plasma- and thermo-chemistry are important for many fields, including environmental monitoring, forensic analysis, debris analysis in a weapon detonation event, and nucleation physics. Recently, significant efforts have been made to understand the chemical pathways involved in the progression from U atoms to diatoms (UO) and polyatomic molecules (UxOy), employing optical spectroscopy tools and computational modeling. In many studies, laser ablation of U or a U-containing flow reactor are used as a highly resource-efficient, repeatable, tunable, and lab-scale testbed for studying gas-phase oxidation in U plasmas. The spectroscopic analysis of high-temperature gas-phase oxidation of U is challenging due to the congested U spectra, resolution limitations of instrumentation, and the numerous chemical reaction pathways possible. This article focuses on the current understanding and challenges related to studying U plasma chemistry, specifically U gas-phase oxidation and molecular formation, via optical spectroscopy of plasmas and associated computational and spectral modeling. The physical and chemical processes involved in the evolution from U atoms to U oxide molecules to nanoparticles and agglomerates (i.e., debris) are discussed in the context of optical spectroscopic studies. The article concludes by highlighting opportunities for future research efforts based on existing knowledge published in the literature.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Electrochemically induced metal- vs. ligand-based redox changes in mackinawite: identification of a Fe 3+ - and polysulfide-containing intermediate

Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H + , CO 2 and NO 3 - reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n(Fe 2+ S 2- ) (s) was found to oxidize to a Fe 3+ containing FeS phase at -0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe 2+ , Fe 3+ , S 2- and polysulfide (S n 2- ) species, with its composition described as Fe 2+ 1-3x Fe 3+ 2x S 2- 1-y (S n 2- ) y . Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe 2+ Fe 3+ 2 S 2- 4 ) and a ligand-based oxidation path between FeS and pyrite (Fe 2+ (S 2 ) 2- ).

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

Ultrasonic Guided-Wave Scan System Used to Characterize Microstructure and Defects in Ceramic Composites

Ceramic matrix composites (CMCs) are being developed for advanced aerospace propulsion applications to save weight, improve reuse capability, and increase performance. However, mechanical and environmental loads applied to CMCs can cause discrete flaws and distributed microdamage, significantly reducing desirable physical properties. Such microdamage includes fiber/matrix debonding (interface failure), matrix microcracking, fiber fracture and buckling, oxidation, and second phase formation. A recent study (ref. 1) of the durability of a C/SiC CMC discussed the requirement for improved nondestructive evaluation (NDE) methods for monitoring degradation in these materials. Distributed microdamage in CMCs has proven difficult to characterize nondestructively because of the complex microstructure and macrostructure of these materials. This year, an ultrasonic guided-wave scan system developed at the NASA Glenn Research Center was used to characterize various microstructural and flaw conditions in SiC/SiC (silicon carbide fiber in silicon carbide matrix) and C/SiC (carbon fiber in silicon carbide matrix) CMC samples.

Roth, Don J.↗
NASA NTRS2013

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Ahlborg, Nadia L.↗
NASA NTRS2010

Oxidation of TaSi2-Containing ZrB2-SiC Ultra-High Temperature Materials

Hot pressed coupons of composition ZrB2-20 v% SiC-5 v% TaSi2 and ZrB2-20 v% SiC-20 v% TaSi2 were oxidized in stagnant air at temperatures of 1627 and 1927C for one, five and ten 10-minute cycles. The oxidation reactions were characterized by weight change kinetics, x-ray diffraction, and SEM/EDS. Detailed WDS/microprobe quantitative analyses of the oxidation products were conducted for the ZrB2-20 v% SiC-20 v% TaSi2 sample oxidized for five 10-minute cycles at 1927C. Oxidation kinetics and product formation were compared to ZrB2-20 v% SiC with no TaSi2 additions. It was found that the 20 v% TaSi2 composition exhibited improved oxidation resistance relative to the material with no TaSi2 additions at 1627C. However, for exposures at 1927C less oxidation resistance and extensive liquid phase formation were observed compared to the material with no TaSi2 additions. Attempts to limit the liquid phase formation by reducing the TaSi2 content to 5 v% were unsuccessful. In addition, the enhanced oxidation resistance at 1627C due to 20 v% TaSi2 additions was not achieved at the 5 v% addition level. The observed oxidation product evolution is discussed in terms of thermodynamics and phase equilibria for the TaSi2-containing ZrB2-SiC material system. TaSi2-additions to ZrB2-SiC at any level are not recommended for ultra-high temperature (>1900C) applications due to excessive liquid phase formation.

Opila, Elizabeth J.↗
DOE OSTI2025

First-Principles study of interface capture of Ni during high-temperature oxidation of NiCr alloys

The formation of precipitated phases of less reactive metals within an oxide scale during alloy oxidation can disrupt its structural integrity, significantly compromising the protective function of the oxide. To better understand this phenomenon, it is crucial to investigate the atomic-level diffusion mechanisms that drive precipitate formation. In this study, we employ first-principles calculations to examine the diffusion and aggregation of Ni atoms across the NiCr/Cr 2 O 3 interface during the high-temperature oxidation of NiCr alloys. Our results reveal that, in the absence of Cr vacancies, Ni atoms predominantly remain within the NiCr substrate, with minimal migration toward the Cr 2 O 3 layer. However, when Cr vacancies are present at both the NiCr/Cr 2 O 3 interface and within the Cr 2 O 3 bulk, Ni atoms exhibit a strong propensity to migrate from the NiCr substrate into the Cr 2 O 3 bulk, where they aggregate into Ni-rich regions with a corundum structure. This study provides valuable atomic-level insights into the diffusion and aggregation of less-reactive metals at the alloy/oxide interface, enhancing our understanding of solute capture and its contribution to the degradation of oxidation resistance in alloys.

Chen, Jianmin [Xiangtan University (China)] (ORCID↗
DOE OSTI2026

In-situ synchrotron X-ray investigation of phase evolution in gas atomized powder enabling manufacturing of nanoscale oxide-dispersion strengthened ferritic steels

Here, we present an investigation of Fe-14Cr-3W-0.4Y-0.4Zr-0.18Ti (wt.%) as a reduced-activation oxide-dispersion strengthened (ODS) ferritic steel, an alternative to the “14YWT” structural alloys designed for nuclear energy applications. Gas atomization reaction synthesis (GARS) was used to produce these Zr-modified powders with a non-equilibrium (metastable) phase that enable a heat treatment (delayed) route for producing nanoscale oxide-dispersion strengthening. In situ synchrotron X-ray diffraction and transmission electron microscopy were used to analyze phase evolution as a function of temperature and time, revealing formation of highly dispersed oxide nanoprecipitate phases at temperatures above those needed for powder consolidation and shaping of components. This would allow fabrication of net-shape parts using conventional powder-processing methods prior to thermal activation of a reaction producing nanocrystalline Y-(Ti, Zr)-O particles, with a size of 20 ± 7 nm. These results can inform processing of tubes, cladding, sheets, and plates for use in advanced fission and fusion reactors.

In-situ synchrotron X-ray diffraction↗
NASA NTRS1995

Effect of KOH concentration and anions on the performance of Ni-H2 battery positive plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galavanostatic charging; and discharging in a flooded electrolyte cell. Three different concentrations of KOH (40 percent, 31 percent, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate or silicate were investigated. The end of charge voltage at C/10 charge and at 10 C showed the following order: 40 percent KOH is greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOE. The middischarge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without the added contaminants and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH where the capacity declined after 1000 cycles at 80 percent DOD. At the end of cycling the plate tested in the presence of sulfate and silicate experienced measurable weight loss as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the second oxidation peak that corresponds to the formation of a different phase of oxidized Ni has a lower peak current at -5 C compared to 25 C and oxygen evolution occurs a higher potential at -5 C. The reduction peak (discharge reaction) is more polarized at 25 C compared to -5 C. The presence of silicate alters the potentials only marginally. The implications of these results in plate treatment and low temperature operation are discussed.

Vaidyanathan, H.↗
DOE OSTI2017

Synthesis and characterization of three-dimensional flower-like tin dioxide-based structures

Three-dimensional flower-like SnO{sub 2}-based structures have been produced by the alkaline hydrothermal treatment of t-SnO{sub 2} powder with no additive and in the presence of aminoterephthalic acid (ATPA). The synthesis products have been characterized by a variety of physicochemical techniques (scanning electron microscopy, transmission electron microscopy, Raman and IR spectroscopies, X-ray diffraction, and others). The results demonstrate that raising the ATPA concentration in the reaction mixture changes the morphology of the materials and leads to the SnO{sub 2} → SnO{sub 2}/Sn{sub 3}O{sub 4} → Sn{sub 3}O{sub 4} phase transformation in the structures through the formation of SnO{sub x} nonstoichiometric tin oxide phases with 1 < x < 2. Hydrothermal treatment of the starting reagents in the presence of ≤75 wt % ATPA leads to the formation of hierarchical structures dominated by a nonstoichiometric tin oxide, which is thermally unstable at t ≥ 500°C. The morphology and phase composition of the synthesized structures have been shown to have a significant effect on the electronic conductivity of the material.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) based on a yttria-stabilized zirconia (YSZ) oxide electrolyte produce hydrogen from water with the assistance of excess thermal energy; however, Sr diffusion within the Gd-doped CeO 2 (GDC) barrier layer during processing or operation can lead to the formation of unwanted secondary phases such as SrO and SrZrO 3 . Here, to establish and compare the degree of impact of these phases on SOEC performance, we conduct first-principles calculations to study their bulk oxide conductivities and compare them to that of the YSZ electrolyte. We find that SrO has a low conductivity arising from the poor mobility and low concentration of mobile oxygen vacancies, and its presence in SOECs should therefore be avoided. SrZrO 3 also has a lower oxide conductivity than YSZ; however, this discrepancy is primarily due to lower vacancy concentrations rather than low mobility. We find that sufficient levels of Y-doping on the Zr site can increase oxygen vacancy concentrations in SrZrO 3 to achieve an oxide ionic conductivity on par with that of YSZ, thereby mitigating any potential deleterious effect on transport performance. Energy-dispersive X-ray spectroscopy confirms that Y is the most common minority element present in SrZrO 3 forming near the GDC–YSZ interface, alleviating concerns regarding the impact of SrZrO 3 on device performance. These results from our combined computational–experimental analysis can inform future engineering strategies designed to limit the detrimental effects of Sr-induced secondary phase formation on SOEC performance.

08 HYDROGEN↗
DOE OSTI2019

An Ordered P2/P3 Composite Layered Oxide Cathode with Long Cycle Life in Sodium-Ion Batteries

Developing stable cathode materials represents a crucial step toward long-life sodium-ion batteries. P2-type layered oxides are important as cathodes for their reversibility, but their long-term performance in full cells remains a key challenge. Herein, we report Na 0.75 Co 0.125 Cu 0.125 Fe 0.125 Ni 0.125 Mn 0.5 O 2 with an intergrowth of ordered P2 and P3 phases, studied by neutron diffraction and Rietveld refinement. A stable electrochemical performance is achieved in Na half cells with 100% capacity retention at a rate of C/10 after 100 cycles (initial capacity of 90 mAh/g), 96% capacity retention at a rate of 1 C after 500 cycles (initial capacity of 70 mAh/g), and 85% capacity retention at a rate of 5 C after 1000 cycles (initial capacity of 55 mAh/g). Stable full cell performance is achieved with 84.2% capacity retention after 1000 cycles at a rate of 1 C. Synchrotron X-ray diffraction, spectroscopy, and imaging are applied to elucidate the relationship between chemical/structural evolution and battery performance. A reversible local and global structural evolution is observed during initial cycles. Meanwhile, the challenges with enabling prolonged cycling (beyond 1000 cycles) may be associated with Fe dissolution and formation of a copper oxide phase. This study implies that cathodes with complex chemical and structural formations may stabilize electrochemical performance and highlights the importance of decoupling the contribution of each transition metal to performance degradation.

25 ENERGY STORAGE↗