Search NASA⌕ Search

SEARCH · Search NASA

Results for “oxidizing environments”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Photosynthesis tunes quantum-mechanical mixing of electronic and vibrational states to steer exciton energy transfer

Significance Photosynthetic light-harvesting antennae transfer energy toward reaction centers with high efficiency, but in high light or oxidative environments, the antennae divert energy to protect the photosynthetic apparatus. For a decade, quantum effects driven by vibronic coupling, where electronic and vibrational states couple, have been suggested to explain the energy transfer efficiency, but questions remain whether quantum effects are merely consequences of molecular systems. Here, we show evidence that biology tunes interpigment vibronic coupling, indicating that the quantum mechanism is operative in the efficient transfer regime and exploited by evolution for photoprotection. Specifically, the Fenna–Matthews–Olson complex uses redox-active cysteine residues to tune the resonance between its excitons and a pigment vibration to steer excess excitation toward a quenching site.

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

Low-Cost, Efficient and Durable High Temperature Wireless Sensors by Direct Write Additive Manufacturing for Application in Fossil Energy Systems

In-situ monitoring of physical parameters in fossil energy (FE) systems is challenging because of their high operating temperatures and oxidizing environments. This research aims utilize Aerosol Jet (AJ) nanoparticle printing, an advanced additive manufacturing method, to fabricate high temperature sensors for FE applications. Sensor films were fabricated by the AJ printing method with an excellent control over film microstructure and properties, in addition to creating less waste. Printing of six different materials, namely, silver (Ag), nickel (Ni), nickel-chromium (NiCr) alloy, copper (Cu), copper-nickel (CuNi), and carbon nanotubes (CNTs) was carried out for their evaluation of as sensor films. The films were then characterized using impedance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS). Film microstructure was correlated with the sensor electrical and mechanical behavior at different temperatures (24-500 °C) and frequencies (0.02 - 300 kHz). This knowledge was then used to fabricate, test, and characterize strain and temperature sensors for high temperature applications. The strain sensors were shown to have a very low thermal strain up to 500 °C and a 57% higher gauge factor compared to the commercially available counterparts. This enhance performance was attributed to the inherent porosity in the sensor films that allowed the films to exhibit a metamaterial-like behavior when deformed. The AJ printed temperature sensors were shown to have the highest Seebeck coefficient amongst all the film-based temperature sensors. In addition, fundamental aspects of crystal structure and phase transformations in Ba(Fe0.7Ta0.3)O3-δ (BFTO), a high temperature sensor material, was investigated along with 3D printed antennas that can transmit sensor signals at high temperatures. Two PhD students, one from first generation college-going underrepresented minority community (URM), two postdoctoral fellows, and several masters and undergraduate students were supported by this award. This work opens up the possibility of realizing low-cost high-performance sensor devices using advanced manufacturing techniques for high temperature FE applications.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

Safety Testing of AGR-5/6/7 Compacts 2-2-2 and 2-2-4

Compacts 2-2-2 and 2-2-4 from the Advanced Gas Reactor (AGR) Fuel Development and Qualification Program’s final irradiation campaign (AGR-5/6/7) were each separately subjected to a thermal soak at 1600°C for 300 h under flowing helium to simulated conditions experienced during a postulated high-temperature gas-cooled reactor (HTGR) depressurization conduction cooldown event. The safety testing of the fuel compacts’ performance under accident conditions was conducted in the Oak Ridge National Laboratory (ORNL) Core Conduction Cooldown Test Facility (CCCTF), which utilizes a stand-alone hot cell at the Irradiated Fuels Examination Laboratory (IFEL). The CCCTF heats fuel to temperatures up to 1900°C in a non-oxidizing environment while continuously monitoring the sweep gas for radioactive 85 Kr to detect release levels associated with hermetic failure of the tristructural-isotropic (TRISO) coating surrounding each fuel kernel. In addition, certain metallic radionuclides that escape the fuel compact are collected on deposition cups that are periodically exchanged with a new cup to obtain information on the overall retention behavior of the TRISO coating layers. Because cesium can diffuse through intact pyrocarbon layers, abnormal degradation of the silicon carbide (SiC) layer in the absence of holistic TRISO coating failure is indicated by release of 134 Cs at levels equivalent to an individual particle inventory in the absence of significant 85 Kr release (Hunn et al. 2014). Additional description of the CCCTF system is provided in Appendix A.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Reliability of Materials and Components for Solid Oxide Fuel Cells

Planar stack solid-oxide fuel cells (SOFCs) require seals that must operate reliably under demanding conditions for lifetimes of 40000 hours. This includes temperature fluctuations between 800°C and RT during on and off cycles, thermal stresses, oxidizing environments and chemical degradation to name a few. This comprehensive report provides results from long term testing of two commercially available multicomponent barium alkali silicate glasses: SCN and G6, chosen as sealing candidates. In this scope, the glass seals were deposited on YSZ and Al 2 O 3 substrates simulating electrolytes (Zrbased) and coatings (both zirconia and Al 2 O 3 ). The seal-substrate couples were subjected to 800°C under air and steam+H 2 +N 2 environments up to 40000 hours to test their integrity under real operating conditions. Extensive studies on the effects of exposure have been conducted over the span of testing at various time intervals. Within the context of characterization, mechanical properties such as density, roughness, thermal expansion and glass transition, viscosity and wettability behavior; and microstructural properties such as glass chemistries, defect formation (cracks and pores), phase transformations (devitrification) and glass-interface reactions are investigated. Results and discussions are provided with a focus on the degradation of the properties over long term interrupted testing.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Phase-Field Modeling of Thermally-Grown Oxide and the Induced Damage Evolution in Environmental Barrier Coatings

The advent of next-generation hydrogen-based engines necessitates materials capable of withstanding temperatures beyond the reach of current superalloys. SiC-based ceramic matrix composites, augmented with environmental barrier coatings (EBCs), present a promising materials solution. Given the active search for effective and durable EBCs, there is a pressing need for modeling tools to understand and predict damage evolution in these materials to help accelerate their development. This study introduces a phase-field model (PFM) designed to simulate the critical role of thermally grown oxides (TGO) in the degradation and failure of EBCs. The model accounts for the severe volume expansion due to oxidation, alongside phase transformations and microstructural evolution during thermal cycling, offering a comprehensive view of the damage processes. Simulation results are validated against experimental findings reported in the literature, establishing the model's potential as a significant tool for understanding and improving the resilience of EBCs in cyclic oxidative environments.

Cheng, Tianle↗
DOE OSTI2025

Phase Field Modeling of Chemical Reaction Related Damage Evolution in Environmental Barrier Coatings

The advent of next-generation engines necessitates materials capable of withstanding temperatures beyond the reach of current superalloys. SiC-based ceramic matrix composites, augmented with environmental barrier coatings (EBCs), present a promising materials solution. Given the active search for effective and durable EBCs, there is a pressing need for modeling tools to understand and predict damage evolution in these materials to help accelerate their development. This study introduces a phase-field model (PFM) designed to simulate the thermally grown oxides (TGO) and phase transformation in the degradation and failure of EBCs. The model accounts for the severe volume expansion due to oxidation, alongside phase transformations and porosity evolution during thermal cycling, offering a comprehensive view of the damage processes. Simulation results are validated against experimental findings reported in the literature, establishing the model's potential as a significant tool for understanding and improving the resilience of EBCs in cyclic oxidative environments.

fast-diffusion path↗
DOE OSTI2022

Fundamental Investigations into the Properties and Performance of Advanced Materials

Intelligent engineering designs require an accurate understanding of material behavior, since any uncertainties or gaps in knowledge must be counterbalanced with heightened factors of safety, leading to overdesign. Therefore, building better structures and pushing the performance of new components requires an improved understanding of the thermomechanical response of advanced materials under service conditions. This dissertation provides fundamental investigations of several advanced materials: thermoset polymers, a common matrix material for fiber-reinforced composites and nanocomposites; aluminum alloy 7075-T6 (AA7075-T6), a high-performance aerospace material; and ceramic matrix composites (CMCs), an advanced composite for extreme-temperature applications. To understand matrix interactions with various interfaces and nanoinclusions at their fundamental scale, the properties of thermoset polymers are studied at the atomistic scale. An improved proximity-based molecular dynamics (MD) technique for modeling the crosslinking of thermoset polymers is carefully established, enabling realistic curing simulations through its ability to dynamically and probabilistically perform complex topology transformations. The proximity-based MD curing methodology is then used to explore damage initiation and the local anisotropic evolution of mechanical properties in thermoset polymers under uniaxial tension with an emphasis on changes in stiffness through a series of tensile loading, unloading, and reloading experiments. Aluminum alloys in aerospace applications often require a fatigue life of over 109 cycles, which is well over ii the number of cycles that can be practically tested using conventional fatigue testing equipment. In order to study these high-life regimes, a detailed ultrasonic cycle fatigue study is presented for AA7075-T6 under fully reversed tension-compression loading. The geometric sensitivity, frequency effects, size effects, surface roughness effects, and the corresponding failure mechanisms for ultrasonic fatigue across different fatigue regimes are investigated. Finally, because CMCs are utilized in extreme environments, oxidation plays an important role in their degradation. A multiphysics modeling methodology is thus developed to address the complex coupling between oxidation, mechanical stress, and oxygen diffusion in heterogeneous carbon fiber-reinforced CMC microstructures.

Schichtel, Jacob J.↗
DOE OSTI2024

A Detailed Reaction Mechanism for Thiosulfate Oxidation by Ozone in Aqueous Environments

The ozone oxidation, or ozonation, of thiosulfate is an important reaction for wastewater processing, where it is used for remediation of mining effluents, and for studying aerosol chemistry, where its fast reaction rate makes it an excellent model reaction. Although thiosulfate ozonation has been studied since the 1950s, challenges remain in developing a realistic reaction mechanism that can satisfactorily account for all observed products with a sequence of elementary reaction steps. Here, we present novel measurements using trapped microdroplets to study the pH-dependent thiosulfate ozonation kinetics. We detect known products and intermediates, including SO32-, SO42-, S3O62-, and S4O62-, establishing agreement with the literature. However, we identify S2O42- as a new reaction intermediate and find that the currently accepted mechanism does not directly explain observed pH effects. Thus, we develop a new mechanism, which incorporates S2O42- as an intermediate and uses elementary steps to explain the pH dependence of thiosulfate ozonation. The proposed mechanism is tested using a kinetic model benchmarked to the experiments presented here, then compared to literature data. We demonstrate good agreement between the proposed thiosulfate ozonation mechanism and experiments, suggesting that the insights in this paper can be leveraged in wastewater treatment and in understanding potential climate impacts.

Deal, Alexandra M↗
DOE OSTI2024

Novel order-level lineage of ammonia-oxidizing archaea widespread in marine and terrestrial environments

Ammonia-oxidizing archaea (AOA) are among the most ubiquitous and abundant archaea on Earth, widely distributed in marine, terrestrial, and geothermal ecosystems. However, the genomic diversity, biogeography, and evolutionary process of AOA populations in subsurface environments are vastly understudied compared to those in marine and soil systems. Here, we report a novel AOA order Candidatus (Ca.) Nitrosomirales which forms a sister lineage to the thermophilic Ca. Nitrosocaldales. Metagenomic and 16S rRNA gene-read mapping demonstrates the abundant presence of Nitrosomirales AOA in various groundwater environments and their widespread distribution across a range of geothermal, terrestrial, and marine habitats. Terrestrial Nitrosomirales AOA show the genetic capacity of using formate as a source of reductant and using nitrate as an alternative electron acceptor. Nitrosomirales AOA appear to have acquired key metabolic genes and operons from other mesophilic populations via horizontal gene transfer, including genes encoding urease, nitrite reductase, and V-type ATPase. The additional metabolic versatility conferred by acquired functions may have facilitated their radiation into a variety of subsurface, marine, and soil environments. We also provide evidence that each of the four AOA orders spans both marine and terrestrial habitats, which suggests a more complex evolutionary history for major AOA lineages than previously proposed. Together, these findings establish a robust phylogenomic framework of AOA and provide new insights into the ecology and adaptation of this globally abundant functional guild.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Synthesis of rhenium coatings on 316 stainless steel and their electrochemical behavior towards water oxidation in saline environments

The production of electrolytic hydrogen or Green Hydrogen has attracted the attention of scientists as a potential enabler of sustainable energy production. The cleavage of the water molecule requires high energy, in order to produce hydrogen and oxygen through their corresponding half reactions, the hydrogen evolution and oxygen evolution reactions. Further, this latter reaction has been studied in more detail, since its slow kinetics make the water electrolysis less efficient, and, for instance, delay the formation of hydrogen in the counter compartment of the electrolytic cell. In this work, a study of the oxygen evolution reaction is presented. For this, a series of rhenium catalysts deposited onto stainless steel 316 are studied with the aim of analyzing the effect of the pure metal (Re) and the metal with heteroatoms (Re-C, Re-B, and Re-O). As one of the problems worldwide is the scarcity of freshwater, the study focuses on the performance of this series of catalysts in highly saline environments, representative of seawater. The synthesis and electrochemical performance is shown, giving high expectations that these electrocatalysts could be potential electrocatalysts in marine environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Color as a tool for quantitative analysis of heterogeneous polymer degradation

Polymers are widely used industry, but degrade due to environmental conditions, such as elevated temperature or radiation. The degradation of polymers is dominated oxidation in oxygenated environments. Such oxidation is commonly referred to as thermal-oxidation or photo-oxidation and in many situations is heterogeneous through thickness of the polymer. While heterogeneous oxidation of polymers is a common phenomenon, the effect on the lifetime of polymers is not well understood as methods to evaluate such oxidation are time consuming and challenging to implement. Here we show a novel method for quantitative evaluation of heterogeneous oxidation in polymers using a fast and accurate color approach. The proposed color approach was observed to improve the efficiency of obtaining heterogenous oxidation profiles in half the time of common approaches, such as indention or Fourier transform infrared spectroscopy. Furthermore, the method was found to produce trends similar to that observed using common approaches and the applicability of the method was verified by mapping oxygen concentration through thickness using energy dispersive X-ray spectroscopy. Lastly, the utility of the proposed method was demonstrated through the generation of an oxidation design space, which is envisioned to assist with designing experiments towards estimation of polymer lifetime. Finally, we anticipate this work to be a starting point for further evaluation of heterogeneous oxidation in polymers using optical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Formal Oxidation States and Coordination Environments in the Catalytic Reduction of CO to Methanol

Fundamental insight into multi-electron, multi-proton redox reactions with organometallic catalysts is greatly facilitated by knowledge of the formal oxidation state of the metal center in each of the elementary reaction steps that comprise the catalytic cycle. X-ray absorption near edge structure (XANES) is utilized herein to quantify the oxidation states and coordination environment of the organometallic resting state and intermediates in a newly proposed catalytic reduction of carbon monoxide to methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The effect of composition, temperature and pressure on the oxidation state and coordination environment of copper in silicate melts

Copper is a redox variable element that may occur as Cu 0 , Cu + , and Cu 2+ in the Earth’s crust. The oxidation state will affect its partitioning between coexisting minerals, melts and fluids and hence its behaviour in magmatic processes. Copper bearing silicate glasses were quenched from melts with 23 synthetic compositions (19 CaO-Na 2 O-MgO-Al 2 O 3 -SiO 2 (CNMAS), two “granites” containing K 2 O ± H 2 O, and Fe-bearing “MORB” and “andesite”) equilibrated at oxygen fugacities (fO 2 ), expressed in log units relative to the fayalite-magnetite-quartz (FMQ) buffer, ranging from −0.7 to 14, temperatures from 900 to 1500 °C and pressures from 0 to 2.5 GPa. Cu K-edge X-ray absorption near edge structure (XANES) spectra were recorded from the glasses and a pre-edge feature in the XANES spectra was found to scale with the proportion of Cu + . Cu + /ΣCu (where ΣCu = Cu + + Cu 2+ ) was quantified by fitting the intensity of the pre-edge feature as a function of fO 2 to the thermodynamically expected relationship. Cu + /ΣCu was found to only weakly depend on melt composition, with more basic melts (e.g., basalts rather than granites) preferentially stabilising Cu 2+ . Increasing temperature stabilises Cu + , while increasing pressure had little effect on Cu + /ΣCu in CNMAS melts but preferentially stabilised Cu 2+ in granite melts. Cu + /ΣCu can be predicted in silicate melts by the empirical equation: log(Cu 2+ /Cu + ) = 0.25(ΔFMQ + 8.58 − 25050/T + 940P/T – 0.02P) − 4.73 + 5400/T + 1.99Λ + (280P – 90P2) where T is temperature in K, P is pressure in GPa and is the optical basicity of the composition. The effects of fO 2 , melt composition, temperature and pressure on Cu + /ΣCu indicate that Cu + will be the dominant oxidation state in terrestrial silicate melts (e.g., Cu + /ΣCu = 99% in an andesitic melt at 900 °C, 1 GPa and ΔFMQ = 1). The electron exchange reaction Cu 2+ + Fe 2+ → Cu + + Fe 3+ occurs on cooling and, given the abundance of Fe in natural melts, the oxidation state of Cu in natural glasses is unlikely to correspond to that in the original melt.

Copper↗
DOE OSTI2022

Effect of Composition and Local Environment on CO 2 Adsorption on Nickel and Magnesium Oxide Solid Solutions

CO 2 adsorption energies on the (100) surfaces of a nickel oxide doped with Mg, magnesium oxide doped with Ni, and their 50:50 solid solution were calculated using density functional theory. The composition and atomic arrangement of the adsorption site was varied to understand how the local environment affects CO 2 adsorption and the basicity of the surfaces at the atomic level. The dispersive and electronic contributions to the adsorption energies were quantified, and the results indicate that the variation of the adsorption energy with adsorption site configuration and metal composition is dominated by electronic interactions. Interestingly, for magnesium oxide doped with nickel, a single substitution can create stronger CO 2 binding sites, which implies stronger basic sites, even though nickel oxide is less basic than magnesium oxide. The effect of double substitution at the binding site can be reasonably approximated by summing the effects of single substitutions. Furthermore, this work provides guidance for the preparation of metal oxides with tailored Lewis basicity.

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

Revealing the etching process of water-soluble Au 25 nanoclusters at the molecular level

Etching (often considered as decomposition) is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. However, the underlying chemistry of their etching process still remains elusive. Here, we use real-time electrospray ionization mass spectrometry to study the reaction dynamics and size/structure evolution of all the stable intermediates during the etching of water-soluble thiolate-protected gold nanoclusters (Au NCs), which reveal an unusual “recombination” process in the oxidative reaction environment after the initial decomposition process. Interestingly, the sizes of NC species grow larger and their ligand-to-metal ratios become higher during this recombination process, which are distinctly different from that observed in the reductive growth of Au NCs (e.g., lower ligand-to-metal ratios with increasing sizes). The etching chemistry revealed in this study provides molecular-level understandings on how metal nanoparticles transform under the oxidative reaction environment, providing efficient synthetic strategies for new NC species through the etching reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

An investigation on the structural stability of $\mathrm{ZIF}$-8 in water versus water-derived oxidative species in aqueous environment

We report the zeolitic-imidazolate-framework-8 (ZIF-8) is one of the extensively studied metal-organic frameworks (MOF) materials because of its unique structure. For its potential applicability in numerous fields, it becomes crucial to have detailed studies on the structural stability of ZIF-8, especially in aqueous environments. A number of studies have been conducted to investigate the breakdown process of the ZIF-8 structure in water; which is known as the hydrolysis of ZIF-8. However, those studies reported different opposing experimental observations on the role of water on the structural stability of ZIF-8, which created obscurity in understanding this phenomenon. This study explored the effects of different water-derived species on the structural stability of ZIF-8; specifically, examined the effects of only water and water with different oxidative species that may be generated by water molecules' dissociation under external energy or catalyst presence. To this effort, we experimentally probed the physical and chemical structural changes of ZIF-8 in DI water and three different solutions of hydrogen peroxides (H 2 O 2 ); taking H 2 O 2 as the source of oxidative species. To assess the changes in elemental compositions, chemical bonds, functional groups, crystal structure, and morphology, all the samples were analyzed by X-ray photoelectron spectroscopy (XPS), energy-dispersive x-ray (EDX) spectroscopy, Fourier Transform Infrared (FTIR) spectroscope, X-ray diffractometer (XRD), and scanning electron microscope (SEM). Significant structural changes in ZIF-8 occurred mainly in the presence of oxidative species in water. Notably, oxidative species' concentration exceeding 1 M heightened the deformation of the ZIF-8 structure.

36 MATERIALS SCIENCE↗