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DOE OSTI2025

Defect Generation and Evolution in Irradiated Epitaxial Films and Heterostructures of Fe 3 O 4 and Cr 2 O 3

Abstract The functionality of nuclear structural materials, sensors, and microelectronics in harsh environments such as radiation relies on understanding defect generation and evolution processes in oxide layers. The initial radiation response of epitaxial thin films of Fe 3 O 4 (111), Cr 2 O 3 (0001), and Fe 3 O 4 (111)/Cr 2 O 3 (0001) heterostructures deposited on Al 2 O 3 (0001) by oxygen‐assisted molecular beam epitaxy and irradiated with 200 keV He + is characterized. X‐ray diffraction and X‐ray absorption near edge spectroscopy showed that the Cr 2 O 3 layers underwent significant lattice expansion and disordering under irradiation, whereas the Fe 3 O 4 layers do not exhibit noticeable changes. In contrast, positron annihilation spectroscopy revealed an evolution of cation vacancy point defects in the Fe 3 O 4 layers into larger vacancy clusters with increasing irradiation, while the cation vacancies in Cr 2 O 3 remained primarily as single vacancies and small clusters. The results suggest that the Fe 3 O 4 lattice can utilize the free volume of the larger vacancy clusters to relax but the small vacancies in the Cr 2 O 3 lattice do not facilitate relaxation. Comparing defect concentrations in the single layer films versus the heterostructure suggests that point defects may cross the interface from Fe 3 O 4 into Cr 2 O 3 . Together, these results enhance the understanding of the initial defect evolution mechanisms in oxide layers in harsh irradiation environments.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Precision measurements on oxygen formation in stellar helium burning with gamma-ray beams and a Time Projection Chamber

The carbon/oxygen (C/O) ratio at the end of stellar helium burning is the single most important nuclear input to stellar evolution theory. However, it is not known with sufficient accuracy, due to large uncertainties in the cross-section for the fusion of helium with 12 C to form 16 O, denoted as 12 C( α , γ ) 16 O. Here we present results based on a method that is significantly different from the experimental efforts of the past four decades. With data measured inside one detector and with vanishingly small background, angular distributions of the 12 C( α , γ ) 16 O reaction were obtained by measuring the inverse 16 O( γ , α ) 12 C reaction with gamma-beams and a Time Projection Chamber (TPC) detector. We agree with current world data for the total reaction cross-section and further evidence the strength of our method with accurate angular distributions measured over the 1 - resonance at E cm ~2.4 MeV. Our technique promises to yield results that will surpass the quality of the currently available data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS2004

A molecular timescale of eukaryote evolution and the rise of complex multicellular life

BACKGROUND: The pattern and timing of the rise in complex multicellular life during Earth's history has not been established. Great disparity persists between the pattern suggested by the fossil record and that estimated by molecular clocks, especially for plants, animals, fungi, and the deepest branches of the eukaryote tree. Here, we used all available protein sequence data and molecular clock methods to place constraints on the increase in complexity through time. RESULTS: Our phylogenetic analyses revealed that (i) animals are more closely related to fungi than to plants, (ii) red algae are closer to plants than to animals or fungi, (iii) choanoflagellates are closer to animals than to fungi or plants, (iv) diplomonads, euglenozoans, and alveolates each are basal to plants+animals+fungi, and (v) diplomonads are basal to other eukaryotes (including alveolates and euglenozoans). Divergence times were estimated from global and local clock methods using 20-188 proteins per node, with data treated separately (multigene) and concatenated (supergene). Different time estimation methods yielded similar results (within 5%): vertebrate-arthropod (964 million years ago, Ma), Cnidaria-Bilateria (1,298 Ma), Porifera-Eumetozoa (1,351 Ma), Pyrenomycetes-Plectomycetes (551 Ma), Candida-Saccharomyces (723 Ma), Hemiascomycetes-filamentous Ascomycota (982 Ma), Basidiomycota-Ascomycota (968 Ma), Mucorales-Basidiomycota (947 Ma), Fungi-Animalia (1,513 Ma), mosses-vascular plants (707 Ma), Chlorophyta-Tracheophyta (968 Ma), Rhodophyta-Chlorophyta+Embryophyta (1,428 Ma), Plantae-Animalia (1,609 Ma), Alveolata-plants+animals+fungi (1,973 Ma), Euglenozoa-plants+animals+fungi (1,961 Ma), and Giardia-plants+animals+fungi (2,309 Ma). By extrapolation, mitochondria arose approximately 2300-1800 Ma and plastids arose 1600-1500 Ma. Estimates of the maximum number of cell types of common ancestors, combined with divergence times, showed an increase from two cell types at 2500 Ma to approximately 10 types at 1500 Ma and 50 cell types at approximately 1000 Ma. CONCLUSIONS: The results suggest that oxygen levels in the environment, and the ability of eukaryotes to extract energy from oxygen, as well as produce oxygen, were key factors in the rise of complex multicellular life. Mitochondria and organisms with more than 2-3 cell types appeared soon after the initial increase in oxygen levels at 2300 Ma. The addition of plastids at 1500 Ma, allowing eukaryotes to produce oxygen, preceded the major rise in complexity.

Evolution, Molecular↗

DOE OSTI2020

Facile Decomposition of Organophosphonates by Dual Lewis Sites on a Fe 3 O 4 (111) Film

Dimethyl methylphosphonate (DMMP) is used as a simulant for toxic nerve agents and pesticides, rendering the understanding of surface chemistry requisite to design effective materials for organophosphonate (catalytic) decomposition at room temperature. In this work, DMMP surface chemistry is studied on an iron oxide surface in a very well-defined environment using temperature-programmed reaction, isotopic labeling, scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory. DMMP, (CH 3 O) 2 P(O)(CH 3 ), dissociates to yield methoxy and methyl methylphosphonate, (CH 3 O)P(O) 2 (CH 3 ), on the surface at room temperature. At higher temperatures, dimethyl ether is formed via intramolecular reaction, followed by the formation of formaldehyde and methanol from adsorbed methoxy decomposition during temperature-programmed reaction. Ultimately, stochiometric combustion at 870 K produces CO, H 2 C=O, and CO 2 via reaction with lattice oxygen, with PO x remaining on the surface. Excess oxygen from the bulk is required to drive these higher temperature pathways. Neither hydrolysis nor a photoreaction is observed, when exposing the adsorbed DMMP to water or light above the band gap, respectively. No evolution of P-containing species is detected, indicating efficient trapping of this contaminant. The activity for DMMP decomposition at room temperature is reduced by the accumulation of PO x . However, a significant amount of reaction persists after multiple temperature-programmed reaction experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Asymmetric Reaction Pathways of Conversion-Type Electrodes for Lithium-Ion Batteries

Metal oxides have been actively explored as promising conversion-type electrode materials for lithium ion batteries due to high deliverable capacity but still notorious for poor cyclability, capacity fading, voltage hysteresis, etc. Yet, the fundamental reason for the undesirable properties of metal oxides behind the repetitive conversion process is still obscure. In this work, we take advantage of synchrotron X-ray techniques as well as transmission electron microscopy to monitor the structural changes during both conversion (lithiation) and reconversion (delithiation) reactions. Difference in diffusion rates of lithium and metal plays a decisive role in determining the reaction pathway. We find lithium accommodation and extraction occur via different reaction routes: lithiation follows a kinetically driven way while delithiation adopts a route close to the thermodynamic ground state path. Thermodynamic structural evolution features the formation of an intermediate phase of Li-Metal (M)-O, suggesting lithium removal accompanies with the Li/M ionic exchange and rearrangement of oxygen framework. The slow diffusion of metal ions and the high kinetic and energy barrier for dissociating the intermediate phase are mainly responsible for uncompleted reconversion reaction, evidenced by remaining Li-M-O phase at the end of charge. Imperfect reconversion reaction eventually limits the utilization of lithium ions over the repeated cycling. Furthermore, this work sheds light on structural changes occurring at metal oxides during both conversion and reconversion processes, which is strongly linked with the performances of conversion-type materials in applications.

25 ENERGY STORAGE↗

NASA NTRS2004

On the Measurement of Elemental Abundance Ratios in Inner Galaxy H II Regions

Although abundance gradients in the Milky Way Galaxy certainly exist, details remain uncertain, particularly in the inner Galaxy, where stars and H II regions in the Galactic plane are obscured optically. In this paper we revisit two previously studied, inner Galaxy H II regions: G333.6-0.2 and W43. We observed three new positions in G333.6-0.2 with the Kuiper Airborne Observatory and reobserved the central position with the Infrared Space Observatory's Long Wavelength Spectrometer in far-infrared lines of S++, N++, N+, and O++. We also added the N+ lines at 122 and 205 microns to the suite of lines measured in W43 by Simpson et al.. The measured electron densities range from approx. 40 to over 4000 per cu cm in a single HII region, indicating that abundance analyses must consider density variations, since the critical densities of the observed lines range from 40 to 9000 per cu cm. We propose a method to handle density variations and make new estimates of the S/H and N/H abundance ratios. We find that our sulfur abundance estimates for G333.6-0.2 and W43 agree with the S/H abundance ratios expected for the gradient previously reported by Simpson et al., with the S/H values revised to be smaller owing to changes in collisional excitation cross sections. The estimated N/H, S/H, and N/S ratios are the most reliable because of their small corrections for unseen ionization states (< or approx. 10%). The estimated N/S ratios for the two sources are smaller than what would be calculated from the N/H and S/H ratios in our previous paper. If all low excitation H II regions had similar changes to their N/S ratios as a result of adding measurements of N+ to previous measurements of N++, there would be no or only a very small gradient in N/S. This is interesting because nitrogen is considered to be a secondary element and sulfur is a primary element in galactic chemical evolution calculations. We compute models of the two H II regions to estimate corrections for the other unseen ionization states. We find, with large uncertainties, that oxygen does not, have a high abundance, with the result that the N/O ratio is as high (approx. 0.35) as previously reported. The reasons for the uncertainty in the ionization corrections for oxygen are both the non-uniqueness of the H II region models and the sensitivity of these models to different input atomic data and stellar atmosphere models. We discuss these predictions and conclude that only a few of the latest models adequately reproduce H II region observations, including the well-known, relatively-large observed Ne++/O++ ratios in low- and moderate-excitation H II regions.

Simpson, Janet P.↗

NASA NTRS1988

Rate of production, dissolution and accumulation of biogenic solids in the ocean

The equatorial current system, by its response to global circulation changes, provides a unique recording mechanism for long range climatic oscillations. A permanent record of the changes in rate of upwelling and organic production is generated in the equatorial deep sea sediments, particularly by such biogenic components which are unaffected by secondary dissolution. In order to determine the rates of accumulation of various sedimentary components, a reliable differential measurement of age of the strata must be obtained. Various approaches to this problem are reviewed, and sources of error discussed. Secondary dissolution of calcium carbonate introduces a substantial and variable difference between the dissolution-modified, and hence a priori unknown, rate of deposition on one hand and the rate of accumulation, derivable from the observed concentration, on the other. The cause and magnitude of these variations are of importance, particularly since some current dating schemes are based on assumed constancy in the rate of accumulation of this and, in some cases, also all other sedimentary components. The concepts used in rate evaluation are discussed with emphasis on the difference between the state of dissolution, an observable property of the sediment, and the rate of dissolution, a parameter that requires deduction of the carbonate fraction dissolved, and of the time differential. As a most likely cause of the enhanced state of dissolution of the interglacial carbonate sediments is proposed the lowered rates of biogenic production and deposition, which cause longer exposure of the carbonate microfossils to corrosion in the bioturbated surface layer of the sediment. Historical perspective is included in the discussion in view of the dedication of the Symposium to Hans Pettersson, the leader of the Swedish Deep Sea Expedition 1947-1948, an undertaking that opened a new era in deep sea research and planetary dynamics.

NASA Discipline Exobiology↗

NASA NTRS2017

Limits to Creation of Oxygen-Rich Atmospheres on Planets in the Outer Reaches of the Conventional Habitable Zone

Abundant free oxygen appears to be a requirement for macroflora and macrofauna. To the best of our knowledge, a general discussion of which habitable planets are conducive to oxygen has not taken place. Theories for the rise of oxygen fall into 4 categories: (i) It is governed by an intrinsic rate of biological innovation, independent of environmental factors. (ii) It is caused by mantle evolution, probably consequent to secular cooling. (iii) It is caused by hydrogen escape, which irreversibly oxidizes the Earth. (iv) It is Gaia's response to the brightening Sun, its rise prevented until reduced greenhouse gases were no longer needed to maintain a clement climate. All but the first of these make implicit astronomical predictions that can be quantified and made explicit. Here we address the third hypothesis. In this hypothesis hydrogen escape acts like an hourglass that continues until all relevant reduced mineral buffers have been oxidized (titrated, as it were) and the surface made safe for O2. The hypothesis predicts that abundant free O2 will be absent from habitable planets that have not experienced significant hydrogen escape. Where hydrogen escape is modest or insignificant, the atmosphere can be approximated as hydrostatic, which makes assessing radiative cooling by embedded molecules, atoms, and ions such as CO2 and H3+ straightforward. In particular, H2 is efficient at exciting non-LTE CO2 15 micron emission, which makes radiative cooling very effective when H2 is abundant. We can therefore map out the region of phase space in which habitable planets do not lose hydrogen, and therefore do not develop O2 atmospheres. A related matter is the power of radiative cooling by embedded molecules to enforce the diffusion limit to hydrogen escape. This matter in particular is relevant to addressing the empirical observation that rocky planets with thin or negligible atmospheres are rarely or never bigger than approx.1.6 Earth radii.

Zahnle, Kevin↗

NASA NTRS2018

Observations of Organic Chemistry on Titan

Titan is the largest moon of Saturn, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Atmospheric photochemistry results in the production of a wide range of complex organic molecules, including hydrocarbons, nitriles, aromatics and species of possible pre-biotic relevance. Studies of Titan's atmospheric chemistry thus provide a unique opportunity to explore the origin and evolution of complex organic matter in a primitive (terrestrial) planetary atmosphere. Underpinned by laboratory measurements, remote and in-situ observations of hydrocarbons, nitriles and oxygen-bearing species provide important new insights in this regard. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new facility, well suited to the study of molecular emission from Titan's upper and middle-atmosphere. This presentation will focus on detection and mapping of rotational emission lines from molecules including HNC, CO, HC3N, CH3CN, C2H3CN and C2H5CN, as well minor isotopologues. Possible chemical formation pathways for these species will be discussed, and the scope for improved understanding of non-aqueous organic chemistry through laboratory experiments and atmospheric/liquid-phase simulations under Titan-like conditions will be examined [5].

Charnley, Steven B.↗

DOE OSTI2021

Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries

Cation-disordered rocksalt (DRX) materials have emerged as a class of novel high-capacity cathodes for Li-ion batteries. However, commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies have shown that fluorination of DRX cathodes can effectively reduce the oxygen loss and improve the cycling stability; however, the underlying atomic-scale mechanisms remain elusive. Herein, using a combination of electrochemical measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy, we examine the correlation between the electrochemical properties and structural evolution in Mn-redox-based DRX cathodes, Li1.2Ti0.4-xMn0.4+xO2.0-xFx (x = 0 and 0.2). We find that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. We further reveal a novel rocksalt-to-spinel-like structural transformation in the DRX bulk, which surprisingly contributes to a gradual capacity increase during cycling. Our results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.

Li, Linze↗

DOE OSTI2023

Selective thermal evolution of native oxide layer in Nb and Nb$_3$Sn-coated SRF grade Nb: An in-situ angular XPS study

This contribution discusses the results of an in-situ angular XPS study on the thermal evolution of the native oxide layer on Nb3Sn and pure Nb. XPS data were recorded with conventional spectrometers using an AlK(alpha) X-ray source for spectra collected up to 600 C, and an MgK(Alpha) X-rays source for temperatures above 600 C. The effect of the thickness, composition, and thermal stability of that oxide layer is relevant to understanding the functional properties of superconducting radiofrequency (SRF) cavities used in particle accelerators. There is a consensus that oxide plays a role in surface resistance (Rs). The focus of this study is Nb3Sn, which is a promising material that is used in the manufacturing of superconducting radiofrequency (SRF) cavities as well as in quantum sensing, and pure Nb, which was included in the study for comparison. The thermal evolution of the oxide layer in these two materials is found to be quite different, which is ascribed to the influence of the Sn atom on the reactivity of the Nb atom in Nb3Sn films. Nb and Sn atoms in this intermetallic solid have different electronegativity, and the Sn atom can reduce electron density around neighbouring Nb atoms in the solid, thus reducing their reactivity for oxygen. This is shown in the thickness, composition, and thermal stability of the oxide layer formed on Nb3Sn. The XPS spectra were complemented by grazing incident XRD patterns collected using the ESRF synchrotron radiation facility. The results discussed herein shed light on oxide evolution in the Nb3Sn compound and guide its processing for potential applications of the Nb3Sn-based SRF cavities in accelerators and other superconducting devices.

Cano, Arely↗

NASA NTRS2004

Evidence for a Wet, Reduced Martian Interior

Knowledge of the oxygen fugacity and hydrogen content of the source regions of martian meteorites is of paramount importance in constraining phase equilibria, crystallization sequences, and geodynamic processes of the martian interior, as well as models of the planet's evolution. To date, these interpretations have been hindered by the paucity in SNC meteorites of Fe-Ti oxides used in conventional oxybarometry, and by the presence of secondary alteration products that make it impossible to quantify primary hydrogen abundances in SNC minerals and melts based on whole rock samples. We present here the first transmission FTIR spectra of individual mineral grains from SNC meteorites, and interpret those results along with Mossbauer data on mineral separates from the same meteorites. Our goal is to quantify the amount of water and the oxygen fugacity present in the source regions for the rocks comprising the meteorites.

Dyar, M. D.↗

DOE OSTI2024

Programmable Catalyst Structures via Adsorbate-Induced Adatom Assembly

The electronic structure and geometric configuration of oxide-supported metal ions are important coordination properties that can be related to catalytic activity and stability. Herein, we interrogate the coordination environment of mononuclear Pd ions supported on ceria using CO adsorption, infrared vibrational spectroscopy, and DFT modeling. We observed the 15 h continuous co-evolution of a palladium- (2167 cm -1 ) and cerium-carbonyl (2177 cm -1 ) complex by monitoring the $\nu$(CO) infrared region. The slow CO adsorption kinetics were caused by the reactive ligand exchange between an oxygen atom of the support and the CO adsorbate to yield an oxygen vacancy and adsorbed CO 2 . We hypothesize that the co-evolved cerium-carbonyl complex was formed upon CO adsorption at or adjacent to this oxygen vacancy. Our hypothesis was experimentally supported by a dramatic attenuation of the cerium carbonyl signal upon pre-adsorption of water through an apparent competitive adsorption mechanism. The attenuation was also accompanied by a 6 cm -1 redshift of the palladium carbonyl band (2161 cm -1 ) attributed to hydrogen bonding between the carbonyl and a nearby hydroxyl. Characteristic n(CO) stretch frequencies catalogued through CO adsorption onto single crystal ceria by Wöll et al.1 led us to index the cerium carbonyl to the {100} nanofacet of the polycrystalline ceria support. It follows from the observed co-evolution of the two carbonyl complexes that Pd was also adsorbed at the {100} nanofacet. Redeployment of a previously developed DFT model by Ivanova-Shor et al.2 featuring square-planar coordination of Pd2+ at the {100} nanofacet (O 4 Pd) of a Ce 21 O 42 nanoparticle model qualitatively reproduced several experimental observations.

36 MATERIALS SCIENCE↗

NASA NTRS2008

Diversity and Physiology of Siderophilic Cyanobacteria: Implication for the Bioenergetics

Prior to 2.4 Ga, global oceans were likely significantly enriched in soluble iron (Rouxel, Bekker, Edwards, 2005), a condition that is not conducive to the growth of most contemporary mesophilic cyanobacteria (CB). Recent studies of the mechanisms of iron-deficiency stress in CB suggest that contemporary mesophilic freshwater and marine B underwent long-term adaptation to a permanent decrease in soluble iron in the ocean environment (Boyer, et al., 1987; Braun, Hantke, and Koster, 1998). Of all extant environments, iron-depositing hot springs may constitute the most appropriate natural models for analysis of the transition of ancestral cyanobacteria (CB) or protocyanobacteria (PCB) (Olson, 2001) from anoxygenic photosynthesis to oxygenic one and biogeochemical processes in the late Archean and early Paleoproterozoic eras. In particular, Olson (2001) proposed the definition for PCB and postulated that the common ancestor of PCB and CB might well have used Fe(OH)+ as the principal electron donor for CO2 fixation (Widdel, et al., 1993; Ehrenreich and Widdel, 1994; Pierson and Olson, 1989; Olson, 2006). Olson (2001) proposed that the driving force for the evolution of RC2, in addition to RC1, was the necessity to use Fe(OH)+ effectively for CO2 fixation in the absence of reduced sulfur compounds. The global decrease of dissolved environmental reduced iron could have been the driving force for the transition from anoxygenic to oxygenic photosynthesis (Brown et al., 2007). Despite the insights into the ecology, evolutionary biology, paleogeobiochemistry, and astrobiology the examination of iron depositing hot springs (IDHS) could potentially provide, very few studies dedicated to the diversity and physiology of cyanobacteria inhabiting IDHS have been conducted. Here we describe the phylogeny, physiology and ultrastructure and biogeochemical activity of several recent CB isolates from two different greater Yellowstone area IDHS, e.g. LaDuke and Chocolate Pots. Phylogenetic analysis of 16S rRNA genes indicated that 6 of 12 new isolates examined could not be placed within established CB genera. Some of the isolates exhibited pronounced requirements for elevated iron concentrations, with maximum growth rates observed when 0.4-1 mM Fe(3+) was present in the media. However, the pronounced effect of iron limitation on the proliferation of siderophilic CB can be observed only after several passages through iron "free" media. TEM studies of several species of siderophilic CB revealed that the cultures JSC-3 and -11 are probably capable of some sort of pinocytosis of precipitated iron. This phenomenon may explain high tolerance of siderophilic CB to iron deficit. We also found that the stimulation of the growth of siderophilic CB by oxidized iron is accompanied by the decrease of O2 evolution by some species after addition Fe(2+) in iron "free" medium.

Brown, Igor↗

DOE OSTI2024

Unveiling the nucleation and growth of Zr oxide precipitates in internally oxidized Nb3Sn superconductors

We report on atomic-scale analyses of nucleation and growth of Zr oxide precipitates and the microstructural evolution of internally oxidized Nb3Sn wires for high-field superconducting magnet applications, utilizing atom probe tomography (APT), transmission electron microscopy (TEM), and first-principles calculations. APT analyses reveal that oxygen and zirconium are already segregated at grain boundaries (GBs) in the unreacted Nb-1Zr-4Ta (at%) alloy prior to forming Nb3Sn through reacting the Nb alloy with Sn and SnO2. After forming Nb3Sn, Zr oxide precipitates nucleate both at the Nb3Sn/Nb heterophase interfaces and in the Nb3Sn grains, driven by the small solubilities of Zr and O in Nb3Sn compared to their value in Nb. A high number density (Nv) of Zr oxide nanoprecipitates is observed in the Nb3Sn layers, ∼10 23 m −3 , with a mean diameter <10 nm for a heat treatment at 625 °C. Quantitative APT and TEM analyses of the Zr oxide precipitates in the reacted Nb3Sn layers elucidate details of the nucleation, growth, and coarsening processes of the Zr oxide precipitates in Nb3Sn. First-principles calculations and classical nucleation theory are employed to study the nucleation of Zr oxide precipitates in Nb3Sn and to estimate the maximum energy barrier and critical radius for nucleation. Our research unveils the kinetic pathways for nucleation and growth of Zr oxide precipitates and the microstructural evolution of Nb3Sn layers, which helps to understand and improve the superconducting properties of internally oxidized Nb3Sn wires for use in high-field superconducting magnets. •We investigated the nucleation and growth of Zr oxide nanoprecipitates in Nb3Sn superconductors for magnet applications.•APT and TEM analyses reveals the nucleation and growth process of Zr oxide precipitates in Nb3Sn layers.•Classical nucleation theory with DFT is employed to describe the nucleation process of Zr oxide precipitates in Nb3Sn.•We find that the interfacial reactions at Nb/Nb3Sn interface play a critical role in the nucleation of Zr oxide precipitates.•Current study provides a pathway to improve the properties of internally oxidized Nb3Sn superconducting wires.

43 PARTICLE ACCELERATORS↗

NASA NTRS1983

The diffusivity of hydrogen in Nb stabilized stainless steel

The evolution of hydrogen from 347 stainless steel has been studied by using a real time dynamic technique under ultrahigh vacuum conditions. Auger electron spectroscopy was used to determine the surface composition as a function of time and temperature. The surface film on the electropolished samples was found to be approximately 15 A thick and consisted of a carbon-oxygen complex and a metal oxide (FexOy). Upon heating to 400 C, the carbon-oxygen complex desorbed as CO and the remaining oxygen and carbon began to incorporate. Also at this temperature sulfur began to diffuse out of the bulk to the surface and at approximately 800 C formed a complete monolayer. At 900 C, carbon and oxygen virtually disappeared, leaving the monolayer of sulfur as the only surface contaminant. The hydrogen diffusivity was found to follow closely the equation D = 7.01 x 10 to the -7th exp(-48.0/RT) sq m per second over the entire temperature range studied, thus indicating that hydrogen evolution is not significantly affected by the changing surface composition. The somewhat higher value of the diffusivity obtained in this work compared to past measurements in austenitic stainless steels may indicate the importance of sample preprocessing and ultrahigh vacuum conditions in minimizing the effects of surface layers.

Outlaw, R. A.↗

NASA NTRS1985

Advanced research and technology programs for advanced high-pressure oxygen-hydrogen rocket propulsion

A research and technology program for advanced high pressure, oxygen-hydrogen rocket propulsion technology is presently being pursued by the National Aeronautics and Space Administration (NASA) to establish the basic discipline technologies, develop the analytical tools, and establish the data base necessary for an orderly evolution of the staged combustion reusable rocket engine. The need for the program is based on the premise that the USA will depend on the Shuttle and its derivative versions as its principal Earth-to-orbit transportation system for the next 20 to 30 yr. The program is focused in three principal areas of enhancement: (1) life extension, (2) performance, and (3) operations and diagnosis. Within the technological disciplines the efforts include: rotordynamics, structural dynamics, fluid and gas dynamics, materials fatigue/fracture/life, turbomachinery fluid mechanics, ignition/combustion processes, manufacturing/producibility/nondestructive evaluation methods and materials development/evaluation. An overview of the Advanced High Pressure Oxygen-Hydrogen Rocket Propulsion Technology Program Structure and Working Groups objectives are presented with highlights of several significant achievements.

Marsik, S. J.↗

NASA NTRS1985

Advanced research and technology program for advanced high pressure oxygen-hydrogen rocket propulsion

Marsik, S. J.↗