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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Comprehensive investigation of the role of Nb on the oxidation kinetics of Zr-Nb alloys

Zirconium oxidation, and the associated hydrogen pickup, has long been considered the life-limiting degradation mechanism of fuel elements in pressurized-water reactor (PWR) systems. Currently, PWRs use Zr-Nb alloys as the cladding material of choice. However, oxidation kinetics for Zr-Nb alloys can vary greatly depending on the Nb content; moreover, even Zr-Nb with the same composition can exhibit radically different oxidation kinetics if heat treated at different temperatures. To improve the fundamental understanding of the corrosion of Zr-Nb, it is necessary to determine mechanistically how Nb affects the oxidation kinetics of the overall system. To achieve this, nano-beam X-ray absorption near-edge spectroscopy (XANES), energy-dispersive spectroscopy (EDS), transmission electron microscopy (TEM), and modelling using the physically based C4 model have been performed in concert on samples of Zr-1.0Nb annealed at two different temperatures, 580 °C and 720 °C, and oxidized in an autoclave environment. Through TEM/EDS, it has been seen that β-Zr precipitates dissolved upon oxidation, releasing Nb to the surrounding environment, while β-Nb precipitates remain intact and retard oxidation of Nb. Comparison of the XANES results and C4 model predictions illustrate that space charge generated in the oxide can lead to subparabolic oxidation kinetics in Zr-Nb alloys, which have been shown to negatively affect the hydrogen-pickup fraction. However, sufficient Nb in solid solution can become oxidized to compensate this mechanism to maintain parabolic kinetics in select alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Bubble nucleation and migration in a lead-iron hydr(oxide) core-shell nanoparticle

Iron hydroxide is found in a wide range of contexts ranging from biominerals to steel corrosion, and it can transform to anhydrous oxide via releasing O 2 gas and H 2 O. However, it is not well understood how gases transport through a crystal lattice. Here, we present in situ observation of the nucleation and migration of gas bubbles in iron (hydr)oxide using transmission electron microscopy. We create Pb–FeOOH model core–shell nanoparticles in a liquid cell. Under electron irradiation, iron hydroxide transforms to iron oxide, during which bubbles are generated, and they migrate through the shell to the nanoparticle surface. Geometric phase analysis of the shell lattice shows an inhomogeneous stain field at the bubbles. In conclusion, our modeling suggests that the elastic interaction between the core and the bubble provides a driving force for bubble migration.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Effects of heavy metals on biomarkers for oxidative stress in Griffon vulture (Gyps fulvus)

Metals are involved in the formation of reactive oxygen species (ROS) which may result in metal-related oxidative stress that can lead to oxidative damage to lipids, DNA and proteins. It is necessary to understand the mechanisms of metal toxicity in wild birds, and the concentrations that cause effects on oxidative stress biomarkers. The aim of this study is to assess the concentrations of lead (Pb), cadmium (Cd), mercury (Hg), copper (Cu) and zinc (Zn) with regards to oxidative stress in blood samples of 66 Griffon vultures (Gyps fulvus) from two areas of the Autonomous Community of Valencia (East of Spain). The two study areas (Alcoy n=36 and Cinctorres n=30) were selected as random locations of interest that had not yet been studied, and are feeding stations where supplementary food, mainly of pork origin, is provided for vultures. Given that the two study areas are not considered polluted sites, we expected to find low metal concentrations. However, there are no known threshold concentrations at which metals can affect antioxidant systems, and low metal levels may have an effect on antioxidant biomolecules. In this study, since sampling was done at the beginning of the hunting season, the low Pb levels found in most Griffon vultures from Alcoy and Cinctorres (median=12.37 and 16.26 μg/dl, respectively) are suggestive of background levels usually found in vultures that feed on pork carcasses all year round. The ingestion of game meat with bullet fragments in carcasses or with Pb shots embedded in the flesh could be the cause of the high blood Pb concentrations found in three vultures from Cinctorres (83, 290 and 362 μg/dl). Griffon vultures feeding in Cinctorres had enhanced CAT and GST activities and tGSH concentrations, which may be interpreted as protective response against the higher TBARS levels. This study provides threshold concentrations at which metals affect antioxidant system derived from 66 samples of Griffon vulture. Blood Cd concentrations greater than 0.05 μg/dl produced an induction of 33% in GPx and of 44% in CAT activity in erythrocytes of vultures from Alcoy. Hg concentrations in blood higher than 3 μg/dl produced an induction of 10% in SOD activity. Concentrations of Pb above 15 µg/dl in blood produced an inhibition of 12.5% in GPx and 11.3% in CAT activity, and a TBARS induction of 10.7% in erythrocytes of Griffon vultures. - Highlights: • Except for 3 Griffon vultures, lead levels could be considered background levels. • Three vultures may be exposed to meat with bullet fragments (blood Pb=83–362 μg/dl). • Blood Cd levels≥0.05 μg/dl caused an induction of GPx and CAT activity (33% and 44%). • Blood Hg levels≥3 μg/dl caused an induction of 10% in SOD activity. • Blood Pb≥15 µg/dl caused an inhibition of GPx and CAT activity and a TBARS induction.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of this project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites—inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation mechanism may help to explain U retention in some geologic materials, improving our understanding of U-based geochronology and the redox status of ancient geochemical environments. Additionally, U(VI) may be incorporated within silicate minerals though encapsulation of U-bearing iron oxides, leading to a redox stable solid. Our research detailing previously unrecognized mechanism of U incorporation within sediment minerals may even lead to new approaches for in situ contamination remediation techniques, and will help refine models of U fate and transport in reduced subsurface zones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Improvement in oxidation resistance of the leading edge thermal protection for a space shuttle

To improve the oxidation resistance of a carbon-carbon composite, impregnations were performed using pitches, polyfurfuryl alcohols, and phenolic resins, including a silicon-doped phenolic resin. Oxidation resistance and strength increased for all of the composites as the impregnant-carbon residue increased. The properties of the composites impregnated with the nonsilicon-bearing resins were nearly identical and depended only on the amount of impregnant residue present. However, for equivalent residue concentrations, composites produced with the silicon-bearing resin gave higher strengths and at least 100% better oxidation resistance than was observed for the other composites or for a prototype control material.

Williams, J. M.↗
DOE OSTI2014

Invariant bandwidth of erbium in ZnO-PbO-tellurite glasses: Local probe/model

A series of [(70TeO{sub 2}−(30−x)ZnO−xPbO){sub 0.99}−(Er{sub 2}O{sub 3}){sub 0.01}; where x = 5, 10, 15 and 20] tellurite glasses, were prepared using the melt quenching technique. Crucial emission bandwidth of erbium at 1.5 μm has been derived and found to be the same for all the glasses, irrespective of PbO content. This identical bandwidth in all tellurite glasses is attributed to the presence of erbium in tellurium rich disordered environments. This result has been complemented through XANES spectra and the obtained invariant first shell of 6.5 oxygen atoms, confirm the unchanged environment in these glasses for all PbO content.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Study of Cu and Pb partitioning in mine tailings using the Tessier sequential extraction scheme

The Cu and Pb partitioning in nonferrous mine tailings was investigated using the Tessier sequential extraction scheme. The contents of Cu and Pb found in the five operationally defined fractions were determined by inductively coupled plasma optical emission spectrometry. The results showed different partitioning patterns for Cu and Pb in the studied tailings. The total Cu and Pb contents were higher in tailings from Brazesti than in those from Saliste, while the Cu contents in the first two fractions considered as mobile were comparable and the content of mobile Pb was the highest in Brazesti tailings. In the tailings from Saliste about 30% of Cu and 3% of Pb were found in exchangeable fraction, while in those from Brazesti no metals were found in the exchangeable fraction, but the percent of Cu and Pb found in the bound to carbonate fraction were high (20% and 26%, respectively). The highest Pb content was found in the residual fraction in Saliste tailings and in bound to Fe and Mn oxides fraction in Brazesti tailings, while the highest Cu content was found in the fraction bound to organic matter in Saliste tailings and in the residual fraction in Brazesti tailings. In case of tailings of Brazesti medium environmental risk was found both for Pb and Cu, while in case of Saliste tailings low risk for Pb and high risk for Cu were found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Investigations on the structure of Pb-Ge-Se glasses

Chalcogenide glasses have attracted much attention because of their potential application in various solid state devices. In the present work, we report here the detailed thermal, structural, microstructural studies on Pb{sub x}Ge{sub 42-x}Se{sub 58} with (0 ≤ x ≤ 20) glasses. The influence of Pb content on the glass transition temperature, specific heat, and non-reversing enthalpy is observed and discussed qualitatively The Raman spectroscopic studies on the all the glass compositions are carried out and deconvoluted into different structural units. The positron annihilation life-time spectroscopy (PALS) studies helped to understand the nature of defect states present in the glassy system and its variation with Pb content. The concentration of charged defect centers is found to increase, whereas the open volume defect concentration decreases with Pb content in these glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Environmental and health impacts of fine and ultrafine metallic particles: Assessment of threat scores

This study proposes global threat scores to prioritize the harmfulness of anthropogenic fine and ultrafine metallic particles (FMP) emitted into the atmosphere at the global scale. (Eco)toxicity of physicochemically characterized FMP oxides for metals currently observed in the atmosphere (CdO, CuO, PbO, PbSO{sub 4}, Sb{sub 2}O{sub 3}, and ZnO) was assessed by performing complementary in vitro tests: ecotoxicity, human bioaccessibility, cytotoxicity, and oxidative potential. Using an innovative methodology based on the combination of (eco)toxicity and physicochemical results, the following hazard classification of the particles is proposed: CdCl{sub 2}∼CdO>CuO>PbO>ZnO>PbSO{sub 4}>Sb{sub 2}O{sub 3}. Both cadmium compounds exhibited the highest threat score due to their high cytotoxicity and bioaccessible dose, whatever their solubility and speciation, suggesting that cadmium toxicity is due to its chemical form rather than its physical form. In contrast, the Sb{sub 2}O{sub 3} threat score was the lowest due to particles with low specific area and solubility, with no effects except a slight oxidative stress. As FMP physicochemical properties reveal differences in specific area, crystallization systems, dissolution process, and speciation, various mechanisms may influence their biological impact. Finally, this newly developed and global approach could be widely used in various contexts of pollution by complex metal particles and may improve risk management. - Highlights: • Seven micro- and nano- monometallic characterized particles were studied as references. • Bioaccessibility, eco and cytotoxicity, and oxidative potential assays were performed. • According to calculated threat scores: CdCl{sub 2}∼CdO>CuO>PbO>ZnO>PbSO{sub 4}>Sb{sub 2}O{sub 3}.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

MAPK pathway activation by chronic lead-exposure increases vascular reactivity through oxidative stress/cyclooxygenase-2-dependent pathways

Chronic exposure to low lead concentration produces hypertension; however, the underlying mechanisms remain unclear. We analyzed the role of oxidative stress, cyclooxygenase-2-dependent pathways and MAPK in the vascular alterations induced by chronic lead exposure. Aortas from lead-treated Wistar rats (1st dose: 10 μg/100 g; subsequent doses: 0.125 μg/100 g, intramuscular, 30 days) and cultured aortic vascular smooth muscle cells (VSMCs) from Sprague Dawley rats stimulated with lead (20 μg/dL) were used. Lead blood levels of treated rats attained 21.7 ± 2.38 μg/dL. Lead exposure increased systolic blood pressure and aortic ring contractile response to phenylephrine, reduced acetylcholine-induced relaxation and did not affect sodium nitroprusside relaxation. Endothelium removal and L-NAME left-shifted the response to phenylephrine more in untreated than in lead-treated rats. Apocynin and indomethacin decreased more the response to phenylephrine in treated than in untreated rats. Aortic protein expression of gp91(phox), Cu/Zn-SOD, Mn-SOD and COX-2 increased after lead exposure. In cultured VSMCs lead 1) increased superoxide anion production, NADPH oxidase activity and gene and/or protein levels of NOX-1, NOX-4, Mn-SOD, EC-SOD and COX-2 and 2) activated ERK1/2 and p38 MAPK. Both antioxidants and COX-2 inhibitors normalized superoxide anion production, NADPH oxidase activity and mRNA levels of NOX-1, NOX-4 and COX-2. Blockade of the ERK1/2 and p38 signaling pathways abolished lead-induced NOX-1, NOX-4 and COX-2 expression. Results show that lead activation of the MAPK signaling pathways activates inflammatory proteins such as NADPH oxidase and COX-2, suggesting a reciprocal interplay and contribution to vascular dysfunction as an underlying mechanisms for lead-induced hypertension. - Highlights: • Lead-exposure increases oxidative stress, COX-2 expression and vascular reactivity. • Lead exposure activates MAPK signaling pathway. • ROS and COX-2 activation by MAPK in lead exposure • Relationship between vascular ROS and COX-2 products in lead exposure.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Electronic Rearrangement in Steps of Reductive Elimination of Polar Electrophiles Leads to Refinement of Redox Events

The oxidative addition/reductive elimination of polar molecules such as methyl iodide at late metal centers has a strongly supported $S_{N^2}$ mechanism for many key organometallic complexes, including important industrial catalysts. In the reductive elimination direction, it is proposed that a ligand initially dissociates, typically a halide, followed by subsequent nucleophilic attack at the ligand trans to the now vacant site. The prevailing view is the metal reduction occurs upon transferring the electrophile in the $S_{N^2}$ step. Herein, we report the use of an ensemble of computational techniques to characterize the electronic structure of the reactants and intermediates along this reductive elimination pathway. These calculations demonstrate, unexpectedly, that the initiating loss of an anionic ligand from the octahedral highly oxidized structure leads to an electronic rearrangement that shifts electron density from the apical ligand back toward the metal resulting in an inversion of the electron flow between the metal and apical ligand. The anisotropic shift in electron density to the metal disproportionately affects the apical position, which is best described as a Pt → Me dative bond. With this Pt → Me bonding description, our interpretation of the IUPAC oxidation state formalism would assign the intermediate as Pt ΙΙ . Although counterintuitive, the formal and functional reduction of the metal thus occurs upon halide dissociation.

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

3D Microscopy to Assess the Effect of High Temperature Cyclic Oxidation on the Deformation of Cast and ODS FeCrAlY Alloys

Specimen deformation, oxide scale growth, and scale cracking were monitored for cyclic oxidation exposures at 1200 °C of three cast FeCrAlY(Hf) alloys and two oxide dispersion strengthened (ODS) FeCrAl alloys. Evolution of both the specimen geometry and surface deformation was quantified using 3D optical microscopy. The stress in the alumina scale was also measured using photo-stimulated luminescence piezospectroscopy. The goal was to examine the effect of stress generation and stress relaxation on scale spallation for FeCrAl materials with drastic differences in terms of high temperature strengths. After 1000, 1-h cycles, the cast alloys exhibited significant deformation with a convoluted oxide scale, leading for the two Hf-free FeCrAlY alloys to undergo crack formation and spallation. For the Hf-containing FeCrAlY, limited spallation was observed due to the localization of spallation at grain boundaries, the large grain structure, and the beneficial effect of Hf on scale adhesion. On the other hand, limited deformation was measured for the ODS FeCrAl alloys, with minimal cracking and scale spallation for alloy PM2000 after 1000 h. A higher spallation rate was observed for ODS MA956, which was attributed to a high defect concentration in the alumina scale that formed. The mechanisms leading to spallation during cyclic oxidation for the cast and ODS FeCrAlY alloys are described.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere

Reducibility is key for the use of bulk metal oxides in chemical transformation involving redox reactions but probing microscopic processes of oxide reduction is challenging. This is because the insulating nature of bulk oxides restricts ion and electron spectroscopic measurements of oxide surfaces. Herein, using a combination of environmental transmission electron microscopy and atomistic modeling, we report direct in-situ atomic-scale observations of the surface and subsurface dynamics and show that the hydrogen induced CuO reduction occurs via the surface decay of Cu-O/Cu bilayer atomic steps, formation of partially reduced CuO superstructure by the self-ordering of O vacancies in the subsurface, and collapse of Cu-O layers in the bulk. In this work, all these substeps can be traced back to the progressively increased concentration and activity of O vacancies in the surface and subsurface of the oxide, thereby leading to the self-accelerated oxide reduction. These results demonstrate the microscopic details that may have broader applicability in modulating various redox processes.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Multichannel transition emissions of Dy{sup 3+} in fiber-adaptive germanium tellurite glasses

Multichannel transition visible and near-infrared (NIR) fluorescences have been captured in Dy{sup 3+}-doped fiber-adaptive Na{sub 2}O-ZnO-PbO-GeO{sub 2}-TeO{sub 2} glasses. The maximum stimulated emission cross-sections {sigma}{sub em-max} were derived to be 0.33 Multiplication-Sign 10{sup -21}, 3.66 Multiplication-Sign 10{sup -21}, and 0.67 Multiplication-Sign 10{sup -21} cm{sup 2} for conventional visible emissions assigned to {sup 4}F{sub 9/2}{yields}{sup 6}H{sub J} (J = 15/2, 13/2, and 11/2) transitions, respectively. Infrequent multi-peak NIR emissions were recorded in the spectral range of 900-1500 nm, among which the values of {sigma}{sub em-max} were solved to be 1.05 Multiplication-Sign 10{sup -22} and 1.56 Multiplication-Sign 10{sup -22} cm{sup 2} for {approx}1.02 and {approx}1.18 {mu}m emission bands. Internal quantum efficiency for the {sup 4}F{sub 9/2} level and external quantum yield for visible emissions of Dy{sup 3+} were determined to be 88.44% and 12.38%, severally. Effective multichannel radiative emissions reveal a potential in developing fiber-lighting sources, tunable lasers, and NIR optical amplifiers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Surface and interfacial reaction study of InAs(100)-crystalline oxide interface

A crystalline oxide film on InAs(100) is investigated with in situ monochromatic x-ray photoelectron spectroscopy and low energy electron diffraction before and after in situ deposition of Al{sub 2}O{sub 3} by atomic layer deposition (ALD) as well as upon air exposure. The oxidation process leads to arsenic and indium trivalent oxidation state formation. The grown epitaxial oxide-InAs interface is stable upon ALD reactor exposure; however, trimethyl aluminum decreases oxidation states resulting in an unreconstructed surface. An increase in oxide concentration is also observed upon air exposure suggesting the crystalline oxide surface is unstable.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Effect of applied mechanical stress on absorption coefficient of compounds

The absorption coefficient of given materials is the parameter required for the basic information. The measurement of absorption coefficient of compounds Al{sub 2}O{sub 3}, CaCO{sub 3}, ZnO{sub 2}, SmO{sub 2} and PbO has been taken at different incident photon energies 26, 59.54, 112, 1173, 1332keV. The studies involve the measurements of absorption coefficient of the self supporting samples prepared under different mechanical stress. This mechanical stress is render in terms of pressure up to 0-6 ton by using hydraulic press. Measurements shows that absorption coefficient of a material is directly proportional to applied mechanical stress on it up to some extent then become independent. Experimentally measured results are in fairly good agreement with in theoretical values obtained from WinXCOM.

36 MATERIALS SCIENCE↗