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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Modification of Structural, Chemical and Process Properties of Rare Metal Minerals under Treatment by High-Voltage Nanosecond Pulses

The authors have studied the mechanism of controlled modification of composition, structure, chemistry, physicochemical and process properties of columbite, tantalite, zircon and feldspar at the meso-, micro- and nanoscales after nonthermal treatment by high-voltage nanosecond electromagnetic pulses. The studies used methods: X-ray photoelectron spectroscopy, scanning electron and atomic force microscopy, potentiometric titration, electromigration chromatography, Kelvin probe force microscopy, microhardness metering and assessment of hydrophobic behavior and flotation activity of the minerals. It is found that changes in the chemical state of atoms on the surface of minerals are mainly connected with the sequential transformation of stages in the process of formation and modification of a functional cover of mineral surface, with variation in a ratio of different type hydroxyl groups on the surface of columbite, zircon and feldspar, which conditions contrast physicochemical properties of rare metal minerals and improves selectivity of their separation by flotation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Investigation of the 176 Yb Interference Correction during Determination of the 176 Hf/ 177 Hf Ratio by Laser Ablation and Solution Analysis on the Neoma MC-ICP-MS

We utilized the Neoma™, a recently released MC-ICP-MS platform offered by ThermoFisher Scientific, to assess the behavior of the Lu-Yb-Hf system during laser ablation analyses of various zircon standards as well as solution-based analyses of the JMC-475 Hf standard doped with varying quantities of Yb and Lu. The primary goal of this work was to characterize the behavior of the Yb interference correction on the Neoma™ platform since this is one of the biggest issues in the Hf isotope analysis community and because the Neoma™ platform will supplant the Neptune™ series instrument. During laser ablation analysis, we found that the overall data quality scales proportionally with the total Hf signal intensity, with higher signal analyses producing extremely accurate (within 1 ε Hf unit) and precise (sub ε Hf unit within-run standard errors) data. At low Yb signals (<0.1 V 173 Yb), we were not able to produce an accurate internal Yb mass bias factor. However, utilizing an empirical approach allows for the application of session-specific relationships between the Yb and Hf mass bias factors, determined by analysis of standards of varying Yb content, to produce accurate ε Hf values from zircons with higher Yb/Hf ratios even where the total Hf signal intensity is relatively low. Similar behavior was observed in the solution analyses. Lastly, while the behavior of the Yb interference correction on the Neoma™ platform appears comparable to the Neptune™ series MC-ICP-MS, further work will help refine the understanding of the controls on mass bias behavior, oxide formation, session-to-session stability, etc.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Oxidation state and coordination environment of Pb in U-bearing minerals

This study examines the oxidation and coordination of lead (Pb) in the uranium (U) minerals uraninite (UO 2 ), coffinite (USiO 4 ), and brannerite (UTi 2 O 6 ), and minerals that have U as a minor constituent, zircon (ZrSiO 4 ) and titanite (CaTiSiO 5 ). The characterization of Pb was conducted through a combination of micro-synchrotron X-ray fluorescence mapping (µSXRF) and micro-X-ray absorption spectroscopy (µXAS), collected at the Pb L II and L III edge on characterized grains (electron microscopy and X-ray diffraction) from a range of geological settings and ages. For all minerals considered in this study, Pb L II and L III X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data indicate that Pb exists as Pb 2+ . In the case of uraninite, DFT structure optimization calculations suggest that the substitution of Pb 2+ for U 4+ is facilitated by the stereochemically active electron lone pair indicative of Pb 2+ , which effectively takes the place of an oxygen vacancy (coupled substitution Pb 2+ + = U 4+ + O 2- ). In detail, however, the EXAFS and XANES data, supported by first principle calculations of the XANES associated with Pb 2+ replacing U 4+ in the crystal lattice of uraninite, indicate that Pb 2+ is present in a less distorted coordination than suggested by DFT, which may reflect a yet to be characterized link between interstitial oxygen defects and Pb 2+ incorporation, rather than a simple oxygen vacancy. For coffinite, the XANES data demonstrate that Pb exists mainly as Pb 2+ in the form of galena, indicating limited stability of the isomorphous substitution in coffinite. In contrast, Pb is homogeneously distributed in the metamict mineral brannerite, which displays a distinct XANES spectrum suggestive of Pb 2+ bonded to oxygens in a highly distorted coordination environment. Pb L II XANES indicate that radiogenic Pb exists predominantly as Pb 2+ within the crystal lattice of zircon and as distinct mineral PbO nano-scale inclusions or domains. Additionally, Pb L II XANES measurements also indicate that Pb 2+ exists within titanite although the coordination environment is unclear. Overall, these data suggest that the previous indications of the presence of Pb 4+ in radioactive minerals need to be reconsidered. The nature of radiogenic Pb 2+ incorporation in U-bearing minerals controls the mobilization of Pb in hydrothermal fluids and the utility of a mineral as a geochronometer. The Pb valence and coordination data presented in this study provide fundamental constraints imperative for our understanding of the controls governing the mobilization of radiogenic Pb during water-rock interaction and metamorphism.

58 GEOSCIENCES↗
DOE OSTI2025

Apatite geochemistry as a tool for understanding the petrogenesis of layered mafic-ultramafic rocks in the Bushveld Complex, South Africa

The sources of the magmas that formed the Rustenburg Layered Suite of the Bushveld Complex in South Africa remain debated, despite decades of research. Vertical and lateral variation in bulk rock and mineral separate Sr-Nd isotopic compositions, which generally indicate enriched sources, demonstrate that the layered sequence was formed by the emplacement of multiple batches of magma, crucially resulting in episodes of PGE-Cr-V mineralisation. The Lu-Hf isotope compositions of zircon are, however, at odds with the bulk rock Sr-Nd isotopic heterogeneity as they show near homogeneous compositions throughout the layered sequence (εHf (2.06 Ga) =−8). This lack of variation in Hf isotope composition has been attributed to deep, continental lithospheric mantle-related and/or crustal contamination of plume-derived Bushveld magmas. In this study, we analysed the major, trace element and Sr-Nd isotope geochemistry of apatite in the Rustenburg Layered Suite. Apatite occurs as an intercumulus mineral in the lowermost regions and a cumulus mineral in the uppermost regions of the layered sequence and can therefore be used to test existing models for the isotopic disequilibrium between bulk rock Sr-Nd and zircon Hf isotopic compositions. Apatite is largely chlorapatite in the lowermost regions and fluorapatite in the uppermost regions of the layered sequence. The Merensky Reef is unusual in that it comprises both chlorapatite and fluorapatite. Apatite throughout the layered sequence is generally unzoned and shows no evidence of late-stage alteration. Trace element data show that apatite is enriched in L/HREE, with common negative Eu-Sr anomalies. These trace element signatures are consistent with a magmatic origin for the apatite grains, with prior, or concurrent, plagioclase crystallization from the same melt. Variability in in situ Sr and Nd isotope compositions of apatite is recorded throughout the layered sequence with εNd (2.06 Ga) compositions varying between −2.5 and − 10.2 and initial 87 Sr/ 86 Sr compositions varying between 0.7079 and 0.7103 (for the Marikana dikes only). The variability in Sr-Nd isotope compositions of apatite is consistent with the bulk rock (and mineral separate) variation in Sr-Nd isotope compositions, suggesting apatite preserves primary magmatic compositions in the Rustenburg Layered Suite.

Apatite↗
DOE OSTI2015

Dielectric silicone elastomers with mixed ceramic nanoparticles

Highlights: • Composite ceramics nanoparticles (MCN) with zirconium dioxide and lead zirconate. • Dielectric elastomer films wDith PDMS matrix and MCN as dielectric filler. • Hydrophobic character—water resistant and good flexibility specific to siloxanes. • Increased value of dielectric constant with the content of MCN in dielectric films. • Increased energy output from uniaxial deformation of the dielectric elastomer films. - Abstract: A ceramic material consisting in a zirconium dioxide-lead zirconate mixture has been obtained by precipitation method, its composition being proved by wide angle X-ray powder diffraction and energy-dispersive X-ray spectroscopy. The average diameter of the ceramic particles ranged between 50 and 100 nm, as revealed by transmission electron microscopy images. These were surface treated and used as filler for a high molecular mass polydimethylsiloxane-α,ω-diol (Mn = 450,000) prepared in laboratory, the resulted composites being further processed as films and crosslinked. A condensation procedure, unusual for polydimethylsiloxane having such high molecular mass, with a trifunctional silane was approached for the crosslinking. The effect of filler content on electrical and mechanical properties of the resulted materials was studied and it was found that the dielectric permittivity of nanocomposites increased in line with the concentration of ceramic nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Magnetic resonance in bilayers of ferrite and functionally graded piezoelectric

Highlights: • Ferromagnetic resonance in a ferrite-piezoelectric laminate is studied. • An electric field induced FMR line broadening results from bending the sample. • Ferrite layer between the two piezoelectric layers shows a large line broadening. - Abstract: The particular purpose of this paper is theoretical modeling of magnetoelectric interactions at the ferromagnetic resonance in a layered structure of a ferrite and a piezoelectric with through-thickness graded polarization. We show that using the functionally graded piezoelectric with through-thickness variation of polarization can lead to an electric field induced broadening of ferromagnetic resonance line. As an example, we consider the laminate based on the yttrium iron garnet layer which is placed between two lead zirconate titanate layers with different poling direction. The maximal ferromagnetic resonance line broadening of 9.3 Oe is obtained for the yttrium iron garnet to lead zirconate titanate layer thickness ratio of 1.7 at 9.3 GHz for E equal to 10 kV/cm.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Site Disorder as a Predictor for Compositionally Complex 5RE 2 Zr 2 O 7 Ceramic Phase Stability

Here, phase formation and stability of five component compositionally complex rare earth zirconates (5RE 2 Zr 2 O 7 ) were investigated by X-ray diffraction and electron microprobe analysis. Zirconates with different rare earth compositions (LaNdSmEuDy, LaNdSmEuYb, LaNdEuErYb, LaNdDyErYb, SmEuDyYHo, LaYHoErYb, and DyYHoErYb) were synthesized at 1700°C and 2000°C by the solid-state method to investigate the effect of A-site site disorder (δ A ) on phase stability. Increased site disorder results from mixed cation occupancy with localized crystallographic strain and bond disorder. Compositions LaNdSmEuDy (δ A = 4.6) and LaNdSmEuYb (δ A = 6.0) produced a single pyrochlore phase and compositions SmDyYHoErYb (δ A = 2.8), LaYHoErYb (δ A = 6.2), and DyYHoErYb (δ A = 1.7) produced a single fluorite phase. High δ A compositions LaNdEuErYb (δ A = 6.9) and LaNdDyErYb (δ A = 7.2) produced a pyrochlore and fluorite phase mixture at 1700°C. Single phase was obtained for the latter composition at 2000°C. Of the single phase compositions calcined at 1700°C, LaNdSmEuYb and LaYHoErYb (both with largest δ A ) showed decomposition to mixed fluorite and pyrochlore phases during lower temperature anneals, indicating entropic stabilization. Comparison with prior work shows a temperature dependence of the critical δ A for phase stability, and compositions near it are expected to be entropy stabilized.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Nanomineralogy as a new dimension in understanding elusive geochemical processes in soils: The case of low-solubility-index elements

Nanomineralogical studies of mineral surface coatings in soils reveal insights into biogeochemical processes that heretofore were not known to exist. This is a new dimension in understanding past and present biogeochemical processes in soils, and in this study it is a way to better understand the behavior of low-solubility-index elements such as Al, Ti, and Zr. Soils were sampled from selected sites in Sudbury (Ontario, Canada) that have been affected by acidification and particulate matter emissions from base-metal smelters with subsequent remediation within the past century. These anthropogenic processes have affected an entire landscape, but are now recorded in assemblages of nano-size phases that can be only studied using a combination of focused ion beam technology (for sample preparation) and high-resolution analytical transmission electron microscopy (for phase identification). A first generation of clay minerals (pre-acidification phase), their partial replacement by nano-size hematite and amorphous silica (anthropogenic acidification), and a second generation of clay minerals (post-acidification, including soil remediation) are products of changes in soil biogeochemical processes during these natural and anthropogenic-induced weathering stages. Furthermore, complex assemblages of nanophases formed prior to the second generation of clay minerals depict underlying mechanisms for the mobilization and sequestration of the low-solubility-index elements Zr and Ti under acidic conditions. The occurrence of baddeleyite (ZrO 2 ), anatase (TiO 2 ), and the Magneli phases Ti 4 O 7 and Ti 5 O 9 (all present at the nanoscale) suggest an influx of nanocolloidal Zr and Ti oxides during weathering of smelter-derived particulate matter. Kelyshite {NaZr[Si 2 O 6 (OH)]}, authigenic zircon (ZrSiO 4 ), and kleberite [Fe 3+ Ti 6 O 11 (OH) 5 ] are most likely products of the sequestration of the Zr- and Ti-bearing nanocolloids.

58 GEOSCIENCES↗
DOE OSTI2019

Scalable and Cost-Effective Barrier Layer Coating to Improve Stability and Performance of SOFC Cathode

During this project, a dense GDC barrier layer was deposited on YSZ substrate to prevent chemical reaction between LSCF and YSZ by a cost-effective EPD method. PPy was used as the agent to make YSZ conductive. Highly compact GDC green layer was obtained by the EPD process in an ethanol-based suspension. The deposition rate on PPy coated YSZ is slower than that on graphite because the charge transfer process is the rate-determining step. The main resistance is from the ion accumulation/depletion zone. The H + ions reduced at the cathode consist of free H + ions and absorbed H + ions corresponding to the unavoidable electrochemical reaction and deposition, respectively. A factor f was introduced to reflects EPD efficiency and describe the competitive relationship between deposition and electrochemical reaction during EPD process. f is in the range from 0 to 0.5 which is determined by the amount ration between free H + ions and absorbed H + ions at the suspension/deposit interface and the conductivity of the cathode. f decreases with the increase of current density or applied voltage and the conductivity of the cathode. GDC thin layers formed by DC-EPD in a thickness range of 5-8 µm were successfully densified at as low as 1300 °C and the adhesion between GDC and YSZ was good. The densification temperature can be further reduced to 1250 °C when AC-EPD was used to replace DC-EPD. The deposition rate increases with the increase of duty cycle and voltage ratio. The deposition rate increases with the increase of frequency from 10 Hz to 500 Hz, while decrease when the frequency increases from 500 Hz to 5000 Hz. Desorption of absorbed charge carrier is easy and irreversible. The deposition rate is independent on the conductivity of the cathode when the electrochemical reaction can be ignored with a high frequency. Inter-diffusion of cation ions between the electrolyte and barrier layer has been systematically characterized via 3-D atom probe, TEM, and other techniques. No measurable Sr transport occurs across the GDC layer with a thickness of 1.5 – 6 μm at a LSCF processing temperature of 1000 °C. However, Sr transport does occur across GDC layer with a thickness of 1.5 or 3 μm at a higher LSCF sintering temperature (1000 °C or 1200 °C). The primary pathway are open pores or grain boundaries in the GDC. The observed zirconate layer is discontinuous even for the most extreme conditions (1.5 μm GDC, 1200 °C LSCF sintering temperature). Increasing the thickness of GDC to 4.5 μm can effectively suppress any zirconate formation measurable by SEM-EDX. Cobalt is observed at grain boundaries within the GDC, suggesting some depletion of Co from the LSCF layer that may ultimately impact electrode performance.

08 HYDROGEN↗
DOE OSTI2023

Proton-Conducting Solid Oxide Electrolysis Cells for Large-scale Hydrogen Production at Intermediate Temperatures

Proton-conducting electrolyte based SOECs offer potential for operation at low to intermediate temperatures. Although yttrium-doped barium zirconate (BZY) and ceria-doped barium zirconate (BCY) have conductivity of 0.01 and 0.017 S.cm -1 respectively at 650C in comparison to the conductivity of 0.015 S.cm -1 for 8-YSZ at 850°C, there remains technology gaps and research needs related to understanding of chemical and structural stability in oxidizing and/or reducing atmospheres at intermediate temperatures, material processing and densification techniques, high polarization losses, and electrode poisoning due to intrinsic and extrinsic gas phase contaminants. Synthesis methods have produced proton-conducting materials and cells that met degradation rate targets, showcasing stable hydrogen production. Improved performance was evident in the HSOEC cell, achieving higher hydrogen production at a lower operating temperature compared to standard cells. Collaborations with multiple research facilities ensured scaling up of synthesis processes and milestone achievements for large-scale manufacturing. Assessment of contaminants revealed their adverse effects on electrode performance and structural stability. Contaminants like Cr and Si compounds, in high humidity, degraded electrodes by forming stable silicate and chromates, inhibiting active surface reactions. Getter materials showed promise in capturing contaminants, suggesting potential for mitigation.

08 HYDROGEN↗
NASA NTRS1971

U-Pb ages for sphene in a contact metamorphic zone.

U-Pb ages have been determined on sphene concentrates from the 2700 my old Giants Range Granite at varying distances from the contact with the 1100 my old Duluth gabbro. As the contact is approached the sphene ages become more discordant and plot along a chord between 1100 and 2700 my on a concordia diagram. The U-Pb ages for sphene in the contact aureole are more resistant to thermal metamorphism than are K-Ar ages for hornblende and biotite. The resistance relative to U-Pb ages for zircon is more difficult to interpret because the zircon U-Pb ages may have become discordant prior to or after 1100 my ago, whereas the U-Pb ages for sphene appear to have had episodic discordance only at 1100 my ago.

Hanson, G. N.↗
NASA NTRS1977

Development of Si3N4 and SiC of improved toughness

The application of energy absorbing surface layers to Si3N4 and SiC was investigated. Among the layers studied were microcracked materials such as iron titanate and a silica-zircon mixture and porous materials such as reaction sintered Si3N4. Energy absorption due to microcrack extension upon impact was found not to be an important mechanism. Instead, the fivefold improvement in Charpy and ballistic impact at elevated temperature (1250 C and 1370 C) found for Fe2TiO5 was due to plastic deformation while similar improvement found for silica-zircon mixtures at RT was due to crushing of the porous material. Due to thermal expansion mismatch, these two materials could not withstand thermal cycling when used as energy absorbing surface layers on Si3N4. Reaction sintered Si3N4 layers on dense Si3N4 were found to give up to a sevenfold increase in ballistic impact resistance due to crushing of the layer upon impact. High porosity (45%), large particle size R.S. Si3N4 layers fabricated from -100, +200 mesh Si powder gave better impact improvement than less porous (30%), small particle size layers fabricated from -325 mesh Si powder.

Brennan, J. J.↗
NASA NTRS1981

Lu-Hf total-rock age for the Amitsoq gneisses, West Greenland

Lu-Hf total-rock data for the Amitsoq gneisses of West Greenland yield an age of 3.55 + or - 0.22 billion years, based on the decay constant for Lu-176 of 1.96 x 10 to the -11th/year, and an initial Hf-176/Hf-177 ratio of 0.280482 + or - 33. The result is in good agreement with Rb-Sr total-rock and U-Pb zircon ages. In spite of severe metamorphism of the area at 2.9 billion years, zircons from two of the samples have remained on the total-rock line, and define points close to the initial Hf ratio. The initial Hf-176/Hf-177 lies close to a chondritic Hf isotopic evolution curve from 4.55 billion years to present. This is consistent with the igneous precursors to the Amitsoq gneisses having been derived from the mantle at or shortly before 3.6 billion years. Anomalous relationships between Hf concentration and the Lu-176/Hf-177 ratio may suggest that trace element abundances in the Amitsoq gneisses are partly controlled by processes related to metamorphism.

Pettingill, H. S.↗
NASA NTRS1984

Trace element abundances in megacrysts and their host basalts - Constraints on partition coefficients and megacryst genesis

Rare earth and other trace element abundances are determined in megacrysts of clinopyroxene, orthopyroxene, amphibole, mica, anorthoclase, apatite and zircon, as well as their host basalts, in an effort to gather data on mineral/melt trace element partitioning during the high pressure petrogenesis of basic rocks. Phase equilibria, major element partitioning and isotopic ratio considerations indicate that while most of the pyroxene and amphibole megacrysts may have been in equilibrium with their host magmas at high pressures, mica, anorthoclase, apatite, and zircon megacrysts are unlikely to have formed in equilibrium with their host basalts. It is instead concluded that they were precipitated from more evolved magmas, and have been mixed into their present hosts.

Irving, A. J.↗
NASA NTRS1985

Evolution of basin and range structure in the Ruby Mountains and vicinity, Nevada

Results from various age dating techniques, seismic reflection profiling hydrocarbon maturation studies, and structural analysis were used to evaluate the Cenozoic deformation in the Ruby Mountains and adjoining ranges (pinyon Range and Cortez Range) in Elko and Eureka Counties, Nevada. Age dating techniques used include potassium-argon ages of biotites from granites published by Kistler et al. (1981) and fission track ages from apatite and zircon. Fission track ages from apatite reflect a closing temperature of 100 plus or minus 20 deg C. Zircon fission track ages reflect a closing temperature of 175 plus or minus 25 deg C and potassium-argon ages from brotite reflect a closing temperature of 250 plus or minus 30 deg C. Thus these results allow a reasonably precise tracking of the evolution of the ranges during the Cenozoic. Seismic reflection data are available from Huntington Valley. Access to seismic reflection data directly to the west of the Harrison Pass Pluton in the central Ruby Mountains was obtained. In addition results are available from several deep exploration holes in Huntington Valley.

Blackwell, D. D.↗
NASA NTRS1988

U-Pb ages and Sr, Pb and Nd isotope data for gneisses near the Kolar Schist Belt: Evidence for the juxtaposition of discrete Archean terranes

Uranium-lead ages and Sr, Pb, and Nd isotopic data for gneisses near the Kolar Schist Belt and their interpretation as evidence for the juxtaposition of discrete Archean terranes were presented. The granodioritic Kambha gneiss east of the schist belt has a zircon age of 2532 + or - 3 Ma and mantle-like initial Sr, Pb, and Nd isotopic ratios. Therefore these gneisses are thought to represent new crust added to the craton in the latest Archean. By contrast, more mafic Dod gneisses and leucocratic Dosa gneisses west of the schist belt (2632 + or - 7 and 2610 + or - 10 Ma) show evidence for contamination of their magmatic precursors (LREE-enriched mantle-derived for the Dod gneisses) by older (greater than 3.2 Ga) continental crust. Fragments of this older crust may be present as granitic and tonalitic inclusions in the 2.6-Ga gneisses and in shear zones. The antiquity of these fragments is supported by their Nd, Sr, and Pb isotopic compositions and by 2.8 to greater than 3.2 Ga zircon cores.

Krogstad, E. J.↗