Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

1990-01-01

Advanced oxide thermal barrier coatings have been developed by incorporating multi- component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma- sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia-yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging fiom 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

PubMed

Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

2013-11-01

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

Hydrazines and carbohydrazides produced from oxidized carbon in earth's primitive environment

NASA Technical Reports Server (NTRS)

Folsome, C. E.; Brittain, A.; Smith, A.; Chang, S.

1981-01-01

Whether abiological organic compounds can be formed from the interactions of energy sources with nitrogen, oxidized carbon and water is held to be of importance in geochemical models of the primordial earth atmosphere. It is reported that experiments using quenched spark discharges through molecular nitrogen on aqueous suspensions of CaCO3 and other reactants to simulate the hydrosphere/atmosphere interface yield hydrazine and carbohydrazine in significant but low yields. Such reactions in primitive aquatic environments may have supplied a pathway for chemical evolution and the origin of life, on a primitive earth in which fully oxidized states of carbon were available for the primary synthesis of organic matter.

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

NASA Astrophysics Data System (ADS)

Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

2018-01-01

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

The formation of crystals in glasses containing rare earth oxides

NASA Astrophysics Data System (ADS)

Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

2014-02-01

Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd2O3-22.7CeO2-11.7La2O3-10.9PrO2-1.3Eu2O3-1.3Gd2O3-8.1Sm2O3-4.8Y2O3 with a baseline glass of composition 60.2SiO2-16.0B2O3-12.6Na2O-3.8Al2O3-5.7CaO-1.7ZrO2. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La2O3 and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO5) and oxyapatite (Ca2La8Si6O26) were found in glasses containing La2O3, while oxyapatite (Ca2La8Si6O26 and NaNd9Si6O26) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (TL) of the glasses containing 5%, 10% and 15% La2O3 were 800°C, 959°C and 986°C, respectively; while TL was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients TB2O3, TSiO2, TCaO, and TRE2O3 were also evaluated using a recently published study.

Multifunctional rare-Earth vanadate nanoparticles: luminescent labels, oxidant sensors, and MRI contrast agents.

PubMed

Abdesselem, Mouna; Schoeffel, Markus; Maurin, Isabelle; Ramodiharilafy, Rivo; Autret, Gwennhael; Clément, Olivier; Tharaux, Pierre-Louis; Boilot, Jean-Pierre; Gacoin, Thierry; Bouzigues, Cedric; Alexandrou, Antigoni

2014-11-25

Collecting information on multiple pathophysiological parameters is essential for understanding complex pathologies, especially given the large interindividual variability. We report here multifunctional nanoparticles which are luminescent probes, oxidant sensors, and contrast agents in magnetic resonance imaging (MRI). Eu(3+) ions in an yttrium vanadate matrix have been demonstrated to emit strong, nonblinking, and stable luminescence. Time- and space-resolved optical oxidant detection is feasible after reversible photoreduction of Eu(3+) to Eu(2+) and reoxidation by oxidants, such as H2O2, leading to a modulation of the luminescence emission. The incorporation of paramagnetic Gd(3+) confers in addition proton relaxation enhancing properties to the system. We synthesized and characterized nanoparticles of either 5 or 30 nm diameter with compositions of GdVO4 and Gd0.6Eu0.4VO4. These particles retain the luminescence and oxidant detection properties of YVO4:Eu. Moreover, the proton relaxivity of GdVO4 and Gd0.6Eu0.4VO4 nanoparticles of 5 nm diameter is higher than that of the commercial Gd(3+) chelate compound Dotarem at 20 MHz. Nuclear magnetic resonance dispersion spectroscopy showed a relaxivity increase above 10 MHz. Complexometric titration indicated that rare-earth leaching is negligible. The 5 nm nanoparticles injected in mice were observed with MRI to concentrate in the liver and the bladder after 30 min. Thus, these multifunctional rare-earth vanadate nanoparticles pave the way for simultaneous optical and magnetic resonance detection, in particular, for in vivo localization evolution and reactive oxygen species detection in a broad range of physiological and pathophysiological conditions.

Preliminary reconnaissance survey for thorium, uranium, and rare-earth oxides, Bear Lodge Mountains, Crook County, Wyoming

USGS Publications Warehouse

Wilmarth, V.R.; Johnson, D.H.

1953-01-01

An area about 6 miles north of Sundance, in the Bear Lodge Mountains, in Crook County, Wyo., was examined during August 1950 for thorium, uranium, and rare-earth oxides and samples were collected. Uranium is known to occur in fluorite veins and iron-manganese veins and in the igneous rocks of Tertiary age that compose the core of the Bear Lodge Mountains. The uranium content of the samples ranges from 0.001 to 0.015 percent in those from the fluorite veins, from 0.005 to 0.018 percent in those from the iron-manganese veins, and from 0.001 to 0.017 percent in those from the igneous rocks. The radioactivity of the samples is more than that expected from the uranium content. Thorium accounts for most of this discrepancy. The thorium oxide content of samples ranges from 0.07 to 0.25 percent in those from the iron-manganese veins and from 0.07 to 0.39 percent in those from the sedimentary rocks, and from0.04 to 0.30 in those from the igneous rocks. Rare-earth oxides occur in iron-manganese veins and in zones of altered igneous rocks. The veins contain from 0.16 to 12.99 percent rare-earth oxides, and the igneous rocks, except for two localities, contain from 0.01 to 0.42 percent rare-earth oxides. Inclusions of metamorphosed sedimentary rocks in the intrusive rocks contain from 0.07 to 2.01 percent rare-earth oxides.

Synthesis of nanocrystalline rare earth oxides by glycothermal method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hosokawa, Saburo; Iwamoto, Shinji; Inoue, Masashi

2008-11-03

The reaction of yttrium acetate hydrate in 1,2-propanediol at 300 deg. C yielded a product containing acetate groups and glycol moieties. From this product, Y{sub 2}O{sub 3} was directly crystallized at 400 deg. C without the formation of a carbonate oxide phase. The thus-obtained Y{sub 2}O{sub 3} samples had a small crystallite size (2.2 nm) and significantly large surface area (280 m{sup 2}/g). Other nanocrystalline rare earth (Gd-Yb) oxides were also obtained by this method.

Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth.

PubMed

Catling, D C; Zahnle, K J; McKay, C

2001-08-03

The low O2 content of the Archean atmosphere implies that methane should have been present at levels approximately 10(2) to 10(3) parts per million volume (ppmv) (compared with 1.7 ppmv today) given a plausible biogenic source. CH4 is favored as the greenhouse gas that countered the lower luminosity of the early Sun. But abundant CH4 implies that hydrogen escapes to space (upward arrow space) orders of magnitude faster than today. Such reductant loss oxidizes the Earth. Photosynthesis splits water into O2 and H, and methanogenesis transfers the H into CH4. Hydrogen escape after CH4 photolysis, therefore, causes a net gain of oxygen [CO2 + 2H2O --> CH4 + 2O2 --> CO2 + O2 + 4H(upward arrow space)]. Expected irreversible oxidation (approximately 10(12) to 10(13) moles oxygen per year) may help explain how Earth's surface environment became irreversibly oxidized.

Analysis of “Favorable Growth Element” Based on Rare Earth-aluminum Composite Mechanism of Compound Process

NASA Astrophysics Data System (ADS)

Hao, Baohong; Zeng, Qihui; Zhao, Jin

2018-01-01

Under the background that failure resulted in by high temperature once only aluminum oxide is used as the gasoline additive. This paper, with the purpose to solve this problem, is to synthesize AcAl oxide for gasoline additive. In order to get the rare-earth-aluminum oxide, first, a complex model of rare earth oxide based on theories about ion coordination is established. Then, by the complex model, the type of “compound growth unit” when rare earth elements join the hydrothermal conditions and the inclination that “diversification” might probably happen are deduced. Depending on the results got by complex model, this paper introduces the type of compound and its existence conditions of “Compound growth unit” owned by stable rare-earth-aluminum oxide. By adjusting the compositions of modifier, compound materials of rare earth-aluminum oxide used for gasoline additive is made. By XRD test, aperture test, adsorption test and desorption test, the theoretical deduction is proved to be right. From the experiment, it is concluded that: a dense environment is the pre-condition to form rare-earth-aluminum polymer, which is also an essential condition for the polymer to update to a favorable growth unit and produce mesoporous rare-earth-aluminum oxide with high activity.

Data-driven exploration of copper mineralogy and its application to Earth's near-surface oxidation

NASA Astrophysics Data System (ADS)

Morrison, S. M.; Eleish, A.; Runyon, S.; Prabhu, A.; Fox, P. A.; Ralph, J.; Golden, J. J.; Downs, R. T.; Liu, C.; Meyer, M.; Hazen, R. M.

2017-12-01

Earth's atmospheric composition has changed radically throughout geologic history.1,2 The oxidation of our atmosphere, driven by biology, began with the Great Oxidation Event (GOE) 2.5 Ga and has heavily influenced Earth's near surface mineralogy. Therefore, temporal trends in mineral occurrence elucidate large and small scale geologic and biologic processes. Cu, and other first-row transition elements, are of particular interest due to their variation in valance state and sensitivity to ƒO2. Widespread formation of oxidized Cu mineral species (Cu2+) would not have been possible prior to the GOE and we have found that the proportion of oxidized Cu minerals increased steadily with the increase in atmospheric O2 on Earth's surface (see Fig. 1). To better characterize the changes in Cu mineralogy through time, we have employed advanced analytical and visualization methods. These techniques rely on large and growing mineral databases (e.g., rruff.info, mindat.org, earthchem.org, usgs.gov) and allow us to quantify and visualize multi-dimensional trends.5

A divalent rare earth oxide semiconductor: Yttrium monoxide

NASA Astrophysics Data System (ADS)

Kaminaga, Kenichi; Sei, Ryosuke; Hayashi, Kouichi; Happo, Naohisa; Tajiri, Hiroo; Oka, Daichi; Fukumura, Tomoteru; Hasegawa, Tetsuya

Rare earth sesquioxides like Y2O3 are known as widegap insulators with the highly stable closed shell trivalent rare earth ions. On the other hand, rare earth monoxides such as YO have been recognized as gaseous phase, and only EuO and YbO were thermodynamically stable solid-phase rock salt monoxides. In this study, solid-phase rock salt yttrium monoxide, YO, was synthesized in a form of epitaxial thin film by pulsed laser deposition method. YO possesses unusual valence of Y2+ ([Kr] 4d1) . In contrast with Y2O3, YO was narrow gap semiconductor with dark-brown color. The electrical conductivity was tunable from 10-1 to 103 Ω-1 cm-1 by introducing oxygen vacancies as electron donor. Weak antilocalization behavior was observed indicating significant spin-orbit coupling owing to 4 d electron carrier. The absorption spectral shape implies the Mott-Hubbard insulator character of YO. Rare earth monoixdes will be new platform of functional oxides. This work was supported by JST-CREST, the Japan Society for the Promotion of Science (JSPS) with Grant-in-Aid for Scientific Research on Innovative Areas (Nos. 26105002 and 26105006), and Nanotechnology Platform (Project No.12024046) of MEXT, Japan.

Rare earth doped zinc oxide varistors

DOEpatents

McMillan, A.D.; Modine, F.A.; Lauf, R.J.; Alim, M.A.; Mahan, G.D.; Bartkowiak, M.

1998-12-29

A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2--4.0% oxide of at least one rare earth element, 0.5--4.0% Co{sub 3}O{sub 4}, 0.05--0.4% K{sub 2}O, 0.05--0.2% Cr{sub 2}O{sub 3}, 0--0.2% CaO, 0.00005--0.01% Al{sub 2}O{sub 3}, 0--2% MnO, 0--0.05% MgO, 0--0.5% TiO{sub 3}, 0--0.2% SnO{sub 2}, 0--0.02% B{sub 2}O{sub 3}, balance ZnO. 4 figs.

Rare earth doped zinc oxide varistors

DOEpatents

McMillan, April D.; Modine, Frank A.; Lauf, Robert J.; Alim, Mohammad A.; Mahan, Gerald D.; Bartkowiak, Miroslaw

1998-01-01

A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2-4.0% oxide of at least one rare earth element, 0.5-4.0% Co.sub.3 O.sub.4, 0.05-0.4% K.sub.2 O, 0.05-0.2% Cr.sub.2 O.sub.3, 0-0.2% CaO, 0.00005-0.01% Al.sub.2 O.sub.3, 0-2% MnO, 0-0.05% MgO, 0-0.5% TiO.sub.3, 0-0.2% SnO.sub.2, 0-0.02% B.sub.2 O.sub.3, balance ZnO.

Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

NASA Technical Reports Server (NTRS)

Kasting, James F.

1990-01-01

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

International strategic minerals inventory summary report; rare-earth oxides

USGS Publications Warehouse

Jackson, W.D.; Christiansen, Grey

1993-01-01

Bastnaesite, monazite, and xenotime are currently the most important rare-earth minerals. Bastnaesite occurs as a primary mineral in carbonatites. Monazite and xenotime also can be found in primary deposits but are recovered principally from heavy-mineral placers that are mined for titanium or tin. Each of these minerals has a different composition of the 15 rare-earth elements. World resources of economically exploitable rare-earth oxides (REO) are estimated at 93.4 million metric tons in place, composed of 93 percent in primary deposits and 7 percent in placers. The average mineral composition is 83 percent bastnaesite, 13 percent monazite, and 4 percent of 10 other minerals. Annual global production is about 67,000 metric tons of which 41 percent is from placers and 59 percent is from primary deposits; mining methods consist of open pits (94 percent) and dredging (6 percent). This output could be doubled if the operations that do not currently recover rare earths would do so. Resources are more than sufficient to meet the demand for the predictable future. About 52 percent of the world's REO resources are located in China. Ranking of other countries is as follows: Namibia (22 percent), the United States (15 percent), Australia (6 percent), and India (3 percent); the remainder is in several other countries. Conversely, 38 percent of the production is in China, 33 percent in the United States, 12 percent in Australia, and 5 percent each in Malaysia and India. Several other countries, including Brazil, Canada, South Africa, Sri Lanka, and Thailand, make up the remainder. Markets for rare earths are mainly in the metallurgical, magnet, ceramic, electronic, chemical, and optical industries. Rare earths improve the physical and rolling properties of iron and steel and add corrosion resistance and strength to structural members at high temperatures. Samarium and neodymium are used in lightweight, powerful magnets for electric motors. Cerium and yttrium increase the

Alkaline earth metal doped tin oxide as a novel oxygen storage material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp; Yin, Shu; Yoshida, Mizuki

2015-09-15

Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tinmore » oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.« less

Process for preparing higher oxides of the alkali and alkaline earth metals

NASA Technical Reports Server (NTRS)

Sadhukhan, P.; Bell, A. (Inventor)

1978-01-01

High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

DOE PAGES

Wang, Zhandong; Zhang, Lidong; Moshammer, Kai; ...

2015-12-31

Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS).more » Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C 8H 14O 4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C 8H 16O 5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C 8H 16O 5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O 2 addition, intramolecular isomerization, and OH release; C 8H 14O 4 species are proposed to result from subsequent reactions of C 8H 16O 5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. Furthermore, the results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances.« less

The formation of crystals in glasses containing rare earth oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod

glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients T{sub B2O3}, T{sub SiO2}, T{sub CaO}, and T{sub RE2O3} were also evaluated using a recently published study.« less

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Timing the oxidation of Earth's crust: Evidence from big data records of manganese mineralization

NASA Astrophysics Data System (ADS)

Hummer, D. R.; Golden, J. J.; Hystad, G.; Downs, R. T.; Eleish, A.; Liu, C.; Ralph, J.; Morrison, S.; Meyer, M.; Hazen, R. M.

2017-12-01

A great deal of work has focused on unravelling the oxygenation of Earth's early atmosphere and oceans, which took place during and after the Great Oxidation Event (1). Recently, field and experimental methods have also been used to examine the timing of mantle oxidation, especially near subduction zones (2). However, very little information is available on the timing of crustal oxidation. To examine the oxidation of Earth's shallow crust, we analyzed records of manganese (Mn) mineral occurrences across geologic time from a database of 2666 mineral-locality data pairs (mindat.org as of 20 Nov. 2015) that had associated geologic ages in the literature. Manganese is a redox-sensitive transition element with oxidation states of +2, +3, and +4, whose average oxidation state in the geologic record can be used as a proxy for the oxygenation of the shallow crust, where Mn mineralization typically occurs. Analysis revealed that Mn mineralization older than 600 Ma contained mostly Mn2+ mineral species, with isolated localities containing Mn3+ and Mn4+ species. During the Phanerozoic, the average oxidation state of Mn follows the same trend as reconstructions of atmospheric oxygen (3), but on a 66+1 Myr delay (as calculated using a least squares fitting procedure). This contrasts with a delay of hundreds of millions of years for the oxidation of molybdenum, which forms much deeper in the crust (4). We interpret these time lags as the time necessary to equilibrate various crustal depths to atmospheric oxygen fugacity through infiltration of oxidizing fluids and tectonic mixing processes. Analysis of other redox-sensitive transition metals (such as Cr, V, and Fe) using big data techniques may reveal a strategy for timing the oxidation of different portions of Earth's crust. (1) T.W. Lyons, C.T. Reinhard, N.J. Planavsky, Nature 506, 307-315 (2014). (2) M. Brounce, et al. Geology 43, 775-778 (2015). (3) N.M. Bergman, T.M. Lenton, A.J. Watson, Am. J. Sci. 304, 397-437 (2004). (4

Rare-earth gate oxides for GaAs MOSFET application

NASA Astrophysics Data System (ADS)

Kwon, Kwang-Ho; Yang, Jun-Kyu; Park, Hyung-Ho; Kim, Jongdae; Roh, Tae Moon

2006-08-01

Rare-earth oxide films for gate dielectric on n-GaAs have been investigated. The oxide films were e-beam evaporated on S-passivated GaAs, considering interfacial chemical bonding state and energy band structure. Rare-earth oxides such as Gd 2O 3, (Gd xLa 1- x) 2O 3, and Gd-silicate were employed due to high resistivity and no chemical reaction with GaAs. Structural and bonding properties were characterized by X-ray photoemission, absorption, and diffraction. The electrical characteristics of metal-oxide-semiconductor (MOS) diodes were correlated with material properties and energy band structures to guarantee the feasibility for MOS field effect transistor (FET) application. Gd 2O 3 films were grown epitaxially on S-passivated GaAs (0 0 1) at 400 °C. The passivation induced a lowering of crystallization temperature with an epitaxial relationship of Gd 2O 3 (4 4 0) and GaAs (0 0 1). A better lattice matching relation between Gd 2O 3 and GaAs substrate was accomplished by the substitution of Gd with La, which has larger ionic radius. The in-plane relationship of (Gd xLa 1- x) 2O 3 (4 4 0) with GaAs (0 0 1) was found and the epitaxial films showed an improved crystalline quality. Amorphous Gd-silicate film was synthesized by the incorporation of SiO 2 into Gd 2O 3. These amorphous Gd-silicate films excluded defect traps or current flow path due to grain boundaries and showed a relatively larger energy band gap dependent on the contents of SiO 2. Energy band parameters such as Δ EC, Δ EV, and Eg were effectively controlled by the film composition.

[Mechanical property of tooth-like yttria-stabilized tetragonal zirconia polycrystal by adding rare earth oxide].

PubMed

Gao, Yan; Zhang, Fuqiang; Gao, Jianhua

2012-02-01

To evaluate the influence of mechanical property of tooth-like yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) by adding rare earth oxide as colorants. Six kinds of tooth-like Y-TZP were made by introducing internal coloration technology. The colorants included rare earth oxide (Pr6O11, CeO2, Er2O3) and transition element oxide (MnO2). Mechanical properties (flexural strength, vickers hardness and fracture toughness) were tested. Microstructure was examined by scanning electron microscope(SEM), and the fracture model was analyzed. The range of flexural strength of the six kinds of tooth-like Y-TZP were (792 +/- 20)-(960 +/- 17) MPa, the fracture toughness were (4.72 +/- 0.31)-(5.64 +/- 0.38) MPam(1/2), and the vickers hardness were (1332 +/- 19)-(1380 +/- 17) MPa. SEM observation on the cross section of the six kinds of sintered composites showed a relatively dense polycrystal structure, and the fracture models was mixed type. Tooth-like Y-TZP is acquired with better mechanical properties (fracture toughness and vickers hardness) by adding rare earth oxide as colorants. It is available for clinical application.

A divalent rare earth oxide semiconductor: Yttrium monoxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaminaga, Kenichi; Sei, Ryosuke; Department of Chemistry, Tohoku University, Sendai 980-8578

Rare earth oxides are usually widegap insulators like Y{sub 2}O{sub 3} with closed shell trivalent rare earth ions. In this study, solid phase rock salt structure yttrium monoxide, YO, with unusual valence of Y{sup 2+} (4d{sup 1}) was synthesized in a form of epitaxial thin film by pulsed laser deposition method. YO has been recognized as gaseous phase in previous studies. In contrast with Y{sub 2}O{sub 3}, YO was dark-brown colored and narrow gap semiconductor. The tunable electrical conductivity ranging from 10{sup −1} to 10{sup 3} Ω{sup −1 }cm{sup −1} was attributed to the presence of oxygen vacancies serving as electron donor.more » Weak antilocalization behavior observed in magnetoresistance indicated significant role of spin-orbit coupling as a manifestation of 4d electron carrier.« less

Method of increasing the sulfation capacity of alkaline earth sorbents

DOEpatents

Shearer, J.A.; Turner, C.B.; Johnson, I.

1980-03-13

A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

Method of increasing the sulfation capacity of alkaline earth sorbents

DOEpatents

Shearer, John A.; Turner, Clarence B.; Johnson, Irving

1982-01-01

A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

Tuning charge transfer in the LaTiO3/RO/LaNiO3 (R = rare-earth) superlattices by the rare-earth oxides interfaces from a first-principles calculation

NASA Astrophysics Data System (ADS)

Yao, Fen; Zhang, Lifang; Meng, Junling; Liu, Xiaojuan; Zhang, Xiong; Zhang, Wenwen; Meng, Jian; Zhang, Hongjie

2018-03-01

We investigate the internal charge transfer at the isopolar interfaces in LaTiO3/RO/LaNiO3 (R = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu) superlattices by means of density functional theory calculations. The charge transfer from Ti sites to Ni sites in all superlattices is induced by the electronegativity difference between the elements Ti and Ni, and the lanthanide oxides interfaces can modulate the amount of charge transfer. Comparison of the perovskite heterostructures with the different rare-earth interfaces shows that increasing the deviations of bond angles from 180.0° and the oxygen motions near the interfaces enhance charge transfer. The 4f electrons themselves of rare-earth elements have faint influences on charge transfer. In addition, the reasons why our calculated 4f states of Sm and Tm elements disagree with the experimental systems have been provided. It is hoped that all the calculated results could be used to design new functional nanoelectronic devices in perovskite oxides.

Superconductivity achieved at over liquid nitrogen temperature by (mixed rare earths)-Ba-Cu oxides

NASA Astrophysics Data System (ADS)

Kishio, Kohji; Kuwahara, Kazuyuki; Kitazawa, Koichi; Fueki, Kazuo; Nakamura, Osamu

1987-05-01

Superconducting oxides were fabricated by reaction of powders of BaCO3, CuO and mixed rare earth (RE) carbonates at compositions expressed as (RE)1Ba2Cu3O(9-y). Two types of incompletely separated raw materials of mixed rare earths, namely, heavy rare earths (HRE) and medium rare earths (MRE), were examined. The zero-resistivity critical temperatures were observed at 92.5 K for the (HRE)-Ba-Cu-O and 85.0 K for the (MRE)-Ba-Cu-O systems, respectively, both of which were well above the boiling point of liquid nitrogen.

Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, R.; Rahman, Z.

2015-01-01

The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Taylor, Howard E.; Kimball, B.A.

2004-01-01

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri- n-butyl phosphate–nitric acid adducts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baek, Donna L.; Fox, Robert V.; Case, Mary E.

A new tri- n-butylphosphate–nitric acid (TBP–HNO 3) adduct was prepared by combining TBP and fuming (90%) HNO 3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO 2) was modified with this new adduct [TBP(HNO 3) 5.2(H 2O) 1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO 3 and TBP [TBP(HNO 3) 1.7(H 2O) 0.6]. All rare earth oxides tested with both adduct species couldmore » be extracted with the exception of cerium oxide. Furthermore, the water and acid concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri- n-butyl phosphate–nitric acid adducts

DOE PAGES

Baek, Donna L.; Fox, Robert V.; Case, Mary E.; ...

2016-06-14

A new tri- n-butylphosphate–nitric acid (TBP–HNO 3) adduct was prepared by combining TBP and fuming (90%) HNO 3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO 2) was modified with this new adduct [TBP(HNO 3) 5.2(H 2O) 1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO 3 and TBP [TBP(HNO 3) 1.7(H 2O) 0.6]. All rare earth oxides tested with both adduct species couldmore » be extracted with the exception of cerium oxide. Furthermore, the water and acid concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

The Development of HfO2-Rare Earth Based Oxide Materials and Barrier Coatings for Thermal Protection Systems

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Harder, Bryan James

2014-01-01

Advanced hafnia-rare earth oxides, rare earth aluminates and silicates have been developed for thermal environmental barrier systems for aerospace propulsion engine and thermal protection applications. The high temperature stability, low thermal conductivity, excellent oxidation resistance and mechanical properties of these oxide material systems make them attractive and potentially viable for thermal protection systems. This paper will focus on the development of the high performance and high temperature capable ZrO2HfO2-rare earth based alloy and compound oxide materials, processed as protective coating systems using state-or-the-art processing techniques. The emphasis has been in particular placed on assessing their temperature capability, stability and suitability for advanced space vehicle entry thermal protection systems. Fundamental thermophysical and thermomechanical properties of the material systems have been investigated at high temperatures. Laser high-heat-flux testing has also been developed to validate the material systems, and demonstrating durability under space entry high heat flux conditions.

Theoretical study of the diatomic alkali and alkaline-earth oxides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Theoretical dissociation energies for the ground states of the alkali and alkaline earth oxides are presented that are believed to be accurate to 0.1 eV. The 2 Pi - 2 Sigma + separations for the alkali oxides are found to be more sensitive to basis set than to electron correlation. Predicted 2 Pi ground states for LiO and NaO and 2 Sigma + ground states for RbO and CsO are found to be in agreement with previous theoretical and experimental work. For KO, a 2 Sigma + state is found at both the numerical Hartree-Fock (NHF) level and at the singles plus doubles configuration interaction level using a Slater basis set that is within 0.02 eV of the NHF limit. It is found that an accurate balanced treatment of the two states requires correlating the electrons on both the metal and oxide ion.

Oxidation state of the Earth's upper mantle during the last 3800 million years: Implications for the origin of life

NASA Technical Reports Server (NTRS)

Delano, J. W.

1993-01-01

A popular, as well as scientifically rigorous, scenario for the origin of life on Earth involves the production of organic molecules by interaction of lightning (or other forms of energy) with a chemically reducing atmosphere in the early history of Earth. Experiments since the 1950's have convincingly demonstrated that the yield of organic molecules is high when the atmosphere contains molecular hydrogen, methane, ammonia, and water vapor. Additional work has also shown that such a highly reducing atmosphere might not, however, have been sufficiently long-lived in the presence of intense solar ultraviolet radiation for life to have formed from it. One way of maintaining such an atmosphere would be to have a continual replenishment of the reduced gases by prolonged volcanic outgassing from a reducing of Earth's interior. The length of time that this replenishment might need to continue is in part constrained by the flux of asteroids onto the Earth's surface containing sufficient energy to destroy most, if not all, life that had developed up to that point in time. If a reducing atmosphere is a key ingredient for the origin of life on Earth, the time of the last environmental sterilization due to large impacts would be an important constraint. In a deep marine setting (e.g., hydrothermal vent), the last global sterilization might have occurred at 4200-4000 Ma. On the Earth's surface, the last global sterilization event might have occurred at 4000-3700 Ma. If these are meaningful constraints, how likely is it that a reducing atmosphere could have survived on the Earth until about 3800 Ma ago? Due to the importance of replenishing this atmosphere with reducing components by volcanic outgassing from the mantle, geochemical information on the history of the mantle's oxidation state would be useful for addressing this question. Geochemical and experimental data discussed in this abstract suggest that extrusive mafic volcanics derived from the upper mantle have had

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

NASA Astrophysics Data System (ADS)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

IMPACTS OF ANTIFOAM ADDITIONS AND ARGON BUBBLING ON DEFENSE WASTE PROCESSING FACILITY REDUCTION/OXIDATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jantzen, C.; Johnson, F.

2012-06-05

During melting of HLW glass, the REDOX of the melt pool cannot be measured. Therefore, the Fe{sup +2}/{Sigma}Fe ratio in the glass poured from the melter must be related to melter feed organic and oxidant concentrations to ensure production of a high quality glass without impacting production rate (e.g., foaming) or melter life (e.g., metal formation and accumulation). A production facility such as the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. therefore, themore » acceptability decision is made on the upstream process, rather than on the downstream melt or glass product. That is, it is based on 'feed foward' statistical process control (SPC) rather than statistical quality control (SQC). In SPC, the feed composition to the melter is controlled prior to vitrification. Use of the DWPF REDOX model has controlled the balanjce of feed reductants and oxidants in the Sludge Receipt and Adjustment Tank (SRAT). Once the alkali/alkaline earth salts (both reduced and oxidized) are formed during reflux in the SRAT, the REDOX can only change if (1) additional reductants or oxidants are added to the SRAT, the Slurry Mix Evaporator (SME), or the Melter Feed Tank (MFT) or (2) if the melt pool is bubble dwith an oxidizing gas or sparging gas that imposes a different REDOX target than the chemical balance set during reflux in the SRAT.« less

Molecular electrocatalysts for oxidation of hydrogen using earth-abundant metals: shoving protons around with proton relays.

PubMed

Bullock, R Morris; Helm, Monte L

2015-07-21

the alternate pathway involving oxidation followed by deprotonation. The Mn cation [Mn(P(Ph)2N(Bn)2)(bppm)(CO)](+) mediates the rapid (>10(4) s(-1) at -95 °C), reversible heterolytic cleavage of H2. Obtaining the optimal benefit of pendant amines incorporated into the ligand requires that the pendant amine be properly positioned to interact with a M-H or M(H2) bond. In addition, ligands are ideally selected such that the hydride-acceptor ability of the metal and the basicity of a pendant are tuned to give low barriers for heterolytic cleavage of the H-H bond and subsequent proton transfer reactions. Using these principles allows the rational design of electrocatalysts for H2 oxidation using earth-abundant metals.

Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

PubMed

Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

2016-02-01

The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

Development, characterization and dissolution behavior of calcium-aluminoborate glass wasteforms to immobilize rare-earth oxides.

PubMed

Kim, Miae; Corkhill, Claire L; Hyatt, Neil C; Heo, Jong

2018-03-28

Calcium-aluminoborate (CAB) glasses were developed to sequester new waste compositions made of several rare-earth oxides generated from the pyrochemical reprocessing of spent nuclear fuel. Several important wasteform properties such as waste loading, processability and chemical durability were evaluated. The maximum waste loading of the CAB compositions was determined to be ~56.8 wt%. Viscosity and the electrical conductivity of the CAB melt at 1300 °C were 7.817 Pa·s and 0.4603 S/cm, respectively, which satisfies the conditions for commercial cold-crucible induction melting (CCIM) process. Addition of rare-earth oxides to CAB glasses resulted in dramatic decreases in the elemental releases of B and Ca in aqueous dissolution experiments. Normalized elemental releases from product consistency standard chemical durability test were <3.62·10 -5  g·m -2 for Nd, 0.009 g·m -2 for Al, 0.067 g·m -2 for B and 0.073 g·m -2 for Ca (at 90, after 7 days, for SA/V = 2000m -1 ); all meet European and US regulation limits. After 20 d of dissolution, a hydrated alteration layer of ~ 200-nm-thick, Ca-depleted and Nd-rich, was formed at the surface of CAB glasses with 20 mol% Nd 2 O 3 whereas boehmite [AlO(OH)] secondary crystalline phases were formed in pure CAB glass that contained no Nd 2 O 3 .

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, W.; Flytzani-Stephanopoulos, M.

1996-03-19

A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

The oxidation state of Hadean magmas and implications for early Earth's atmosphere.

PubMed

Trail, Dustin; Watson, E Bruce; Tailby, Nicholas D

2011-11-30

Magmatic outgassing of volatiles from Earth's interior probably played a critical part in determining the composition of the earliest atmosphere, more than 4,000 million years (Myr) ago. Given an elemental inventory of hydrogen, carbon, nitrogen, oxygen and sulphur, the identity of molecular species in gaseous volcanic emanations depends critically on the pressure (fugacity) of oxygen. Reduced melts having oxygen fugacities close to that defined by the iron-wüstite buffer would yield volatile species such as CH(4), H(2), H(2)S, NH(3) and CO, whereas melts close to the fayalite-magnetite-quartz buffer would be similar to present-day conditions and would be dominated by H(2)O, CO(2), SO(2) and N(2) (refs 1-4). Direct constraints on the oxidation state of terrestrial magmas before 3,850 Myr before present (that is, the Hadean eon) are tenuous because the rock record is sparse or absent. Samples from this earliest period of Earth's history are limited to igneous detrital zircons that pre-date the known rock record, with ages approaching ∼4,400 Myr (refs 5-8). Here we report a redox-sensitive calibration to determine the oxidation state of Hadean magmatic melts that is based on the incorporation of cerium into zircon crystals. We find that the melts have average oxygen fugacities that are consistent with an oxidation state defined by the fayalite-magnetite-quartz buffer, similar to present-day conditions. Moreover, selected Hadean zircons (having chemical characteristics consistent with crystallization specifically from mantle-derived melts) suggest oxygen fugacities similar to those of Archaean and present-day mantle-derived lavas as early as ∼4,350 Myr before present. These results suggest that outgassing of Earth's interior later than ∼200 Myr into the history of Solar System formation would not have resulted in a reducing atmosphere.

76 FR 43699 - List of Additional Lands Affected by White Earth Reservation Land Settlement Act of 1985

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-21

... Earth Reservation Land Settlement Act of 1985 AGENCY: Bureau of Indian Affairs, Interior. ACTION: Notice. SUMMARY: This notice lists additional allotments or interest therein on the White Earth Chippewa...) of the White Earth Reservation Land Settlement Act of 1985 (the Act). This notice is required by...

Oxidative Weathering of Earth's Surface 3.7 Billion Years ago? - A Chromium Isotope Perspective

NASA Astrophysics Data System (ADS)

Frei, R.; Crowe, S.; Bau, M.; Polat, A.; Fowle, D. A.; Døssing, L. N.

2015-12-01

The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3-2.9 Gyr ago. 3.8-3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth's earliest surface chemistry and the low oxygen primordial biosphere. We find positive Cr isotope values (average δ53Cr = +0.05 +/- 0.10 permil; δ53Cr = (53Cr/52Cr)sample/(53Cr/52Cr)SRM 979 - 1) x 1000, where SRM 979 denotes Standard Reference Material 979 in both the Fe and Si-rich mesobands of 7 compositionally distinct quartz-magnetite and magnesian banded iron formation (BIF) samples collected from the eastern portion of the Isua BIF (Western Greenland). These postively fractioned Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed BIFs from Isua indicate oxidative Cr cycling 3.8-3.7 Gyr ago. We also examined the distribution of U, which is immobile in its reduced state but mobile when it is oxidized. Elevated U/Th ratios (mean U/Th ratio of 0.70 ± 0.29) in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species (ROS) accumulated in Earth's surface environment inducing the oxidative weathering of rocks during the deposition of the Isua BIFs. The precise threshold atmospheric O2 concentrations for the induction of Cr isotope fractionation remain uncertain, but we argue that our data are consistent with the very low levels of oxygen or other ROS indicated by other proxies. Importantly, any trace of Cr that cycled through redox reactions on land would tend both to be heavy, and to mobilize into the contemporaneous run-off more readily than Cr weathered directly as Cr(III). Once having reached the oceans, this fractionated Cr would have been stripped from seawater by Fe (oxy)hydroxides formed during the deposition of BIFs from low oxygen oceans. The

Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

NASA Technical Reports Server (NTRS)

Kasting, J. F.

1992-01-01

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

Magnetic interactions in new fluorite-related rare earth oxides LnLn’{sub 2}RuO{sub 7} (Ln, Ln’=rare earths)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp; Doi, Yoshihiro

2016-07-15

New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K, which is considerably lowered compared with that for Pr{sub 3}RuO{sub 7}. Analysis of the magnetic specific heat indicates that the magnetic behavior observed at 27 K for Pr{sub 2}YRuO{sub 7} is predominantly due to the magnetic interactions between Ru ions, and that the interactions between the Pr{sup 3+} and Ru{sup 5+} ions are alsomore » important. La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K, which is ascribed to the magnetic ordering between Ru{sup 5+} ions from the analysis of the magnetic specific heat data. - Graphical abstract: New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} show an antiferromagnetic transition at 27 and 9.0 K, respectively. Display Omitted - Highlights: • New fluorite-related quaternary rare earth oxides LnLn’{sub 2}RuO{sub 7} have been prepared. • Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K. • La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K. • Their magnetic exchange mechanism has been elucidated by the magnetic entropy change.« less

A simple enrichment correction factor for improving erosion estimation by rare earth oxide tracers

USDA-ARS?s Scientific Manuscript database

Spatially distributed soil erosion data are needed to better understanding soil erosion processes and validating distributed erosion models. Rare earth element (REE) oxides were used to generate spatial erosion data. However, a general concern on the accuracy of the technique arose due to selective ...

Structure and Abundance of Nitrous Oxide Complexes in Earth's Atmosphere.

PubMed

Salmon, Steven R; de Lange, Katrina M; Lane, Joseph R

2016-04-07

We have investigated the lowest energy structures and binding energies of a series of atmospherically relevant nitrous oxide (N2O) complexes using explicitly correlated coupled cluster theory. Specifically, we have considered complexes with nitrogen (N2-N2O), oxygen (O2-N2O), argon (Ar-N2O), and water (H2O-N2O). We have calculated rotational constants and harmonic vibrational frequencies for the complexes and the constituent monomers. Statistical mechanics was used to determine the thermodynamic parameters for complex formation as a function of temperature and pressure. These results, in combination with relevant atmospheric data, were used to estimate the abundance of N2O complexes in Earth's atmosphere as a function of altitude. We find that the abundance of N2O complexes in Earth's atmosphere is small but non-negligible, and we suggest that N2O complexes may contribute to absorption of terrestrial radiation and be relevant for understanding the atmospheric fate of N2O.

45. VIEW OF UPPER LEVEL CRUSHER ADDITION FROM CRUSHED OXIDIZED ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

45. VIEW OF UPPER LEVEL CRUSHER ADDITION FROM CRUSHED OXIDIZED ORE BIN. 18 INCH BELT CONVEYOR BIN FEED, LOWER CENTER, WITH STEPHENS-ADAMSON 25 TON/HR ELEVATOR SPLIT DISCHARGE (OXIDIZED/UNOXIDIZED) IN CENTER. CRUDE ORE BINS AND MACHINE SHOP BEYOND. NOTE TOP OF CRUSHED OXIDIZED ORE BIN IS BELOW TOP OF CRUDE ORE BINS. - Bald Mountain Gold Mill, Nevada Gulch at head of False Bottom Creek, Lead, Lawrence County, SD

Design of ternary alkaline-earth metal Sn(II) oxides with potential good p-type conductivity

DOE PAGES

Du, Mao -Hua; Singh, David J.; Zhang, Lijun; ...

2016-04-19

Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn 2O 3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn 2O 3 andmore » BaSn 2O 3, which can be stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO 3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn 2O 3) to 3.15 (SrSn 2O 3) eV, and hole effective masses ranging from 0.87 (BaSn 2O 3) to above 6.0 (SrSn 2O 3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.« less

Compound formation and melting behavior in the AB compound and rare earth oxide systems

NASA Astrophysics Data System (ADS)

Huang, Z. K.; Yan, D. S.; Yen, T. S.; Tien, T. Y.

1990-03-01

Compound formation in the systems of the covalent compounds BeO, AlN, and SiC with R2O 3(rare earth oxides) is described. Tentative phase diagrams of the AlN sbnd Nd 2O 3 and AlN sbnd Eu 2O 3 systems are presented.

Effects of rare earth doping on multi-core iron oxide nanoparticles properties

NASA Astrophysics Data System (ADS)

Petran, Anca; Radu, Teodora; Borodi, Gheorghe; Nan, Alexandrina; Suciu, Maria; Turcu, Rodica

2018-01-01

New multi-core iron oxide magnetic nanoparticles doped with rare earth metals (Gd, Eu) were obtained by a one step synthesis procedure using a solvothermal method for potential biomedical applications. The obtained clusters were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray microanalysis (EDX), X-ray photoelectron spectroscopy (XPS) and magnetization measurements. They possess high colloidal stability, a saturation magnetization of up to 52 emu/g, and nearly spherical shape. The presence of rare earth ions in the obtained samples was confirmed by EDX and XPS. XRD analysis proved the homogeneous distribution of the trivalent rare earth ions in the inverse-spinel structure of magnetite and the increase of crystal strain upon doping the samples. XPS study reveals the valence state and the cation distribution on the octahedral and tetrahedral sites of the analysed samples. The observed shift of the XPS valence band spectra maximum in the direction of higher binding energies after rare earth doping, as well as theoretical valence band calculations prove the presence of Gd and Eu ions in octahedral sites. The blood protein adsorption ability of the obtained samples surface, the most important factor of the interaction between biomaterials and body fluids, was assessed by interaction with bovine serum albumin (BSA). The rare earth doped clusters surface show higher afinity for binding BSA. In vitro cytotoxicity test results for the studied samples showed no cytotoxicity in low and medium doses, establishing a potential perspective for rare earth doped MNC to facilitate multiple therapies in a single formulation for cancer theranostics.

Physical and electrochemical properties of alkaline earth doped, rare earth vanadates

NASA Astrophysics Data System (ADS)

Adijanto, Lawrence; Balaji Padmanabhan, Venu; Holmes, Kevin J.; Gorte, Raymond J.; Vohs, John M.

2012-06-01

The effect of partial substitution of alkaline earth (AE) ions, Sr2+ and Ca2+, for the rare earth (RE) ions, La3+, Ce3+, Pr3+, and Sm3+, on the physical properties of REVO4 compounds were investigated. The use of the Pechini method to synthesize the vanadates allowed for high levels of AE substitution to be obtained. Coulometric titration was used to measure redox isotherms for these materials and showed that the addition of the AE ions increased both reducibility and electronic conductivity under typical solid oxide fuel cell (SOFC) anode conditions, through the formation of compounds with mixed vanadium valence. In spite of their high electronic conductivity, REVO4-yttira stabilized zirconia (YSZ) composite anodes exhibited only modest performance when used in SOFCs operating with H2 fuel at 973 K due to their low catalytic activity. High performance was obtained, however, after the addition of a small amount of catalytically active Pd to the anode.

Electronic stopping in oxides beyond Bragg additivity

NASA Astrophysics Data System (ADS)

Sigmund, P.; Schinner, A.

2018-01-01

We present stopping cross sections calculated by our PASS code for several ions in metal oxides and SiO2 over a wide energy range. Input takes into account changes in the valence structure by assigning two additional electrons to the 2p shell of oxygen and removing the appropriate number of electrons from the outer shells of the metal atom. Results are compared with tabulated experimental values and with two versions of Bragg's additivity rule. Calculated stopping cross sections are applied in testing a recently-proposed scaling rule, which relates the stopping cross section to the number of oxygen atoms per molecule.

Giant magnetic anisotropy of rare-earth adatoms and dimers adsorbed by graphene oxide.

PubMed

Zhang, Kai-Cheng; Li, Yong-Feng; Liu, Yong; Zhu, Yan; Shi, Li-Bin

2017-05-24

Nowadays, transition-metal adatoms and dimers with giant magnetic anisotropy have attracted much attention due to their potential applications in data storage, spintronics and quantum computations. Using density-functional calculations, we investigated the magnetic anisotropy of the rare-earth adatoms and dimers adsorbed by graphene oxide. Our calculations reveal that the adatoms of Tm, Er and Sm possess giant magnetic anisotropy, typically larger than 40 meV. When the dimers of (Tm,Er,Sm)-Ir are adsorbed onto graphene oxide, the magnetic anisotropy even exceeds 200 meV. The magnetic anisotropy can be tuned by the external electric field as well as the environment.

Chlorination of UO 2, PuO 2 and rare earth oxides using ZrCl 4 in LiCl-KCl eutectic melt

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

2005-04-01

A new chlorination method using ZrCl 4 in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl 4 has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La 2O 3, CeO 2, Nd 2O 3 and Y 2O 3) and actinide oxides (UO 2 and PuO 2) were allowed to react with ZrCl 4 in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO 2. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl 4 chlorination method, free from corrosive gas, was very simple and useful.

Rare-Earth Oxide (Yb2O3) Selective Emitter Fabrication and Evaluation

NASA Technical Reports Server (NTRS)

Jennette, Bryan; Gregory, Don A.; Herren, Kenneth; Tucker, Dennis; Smith, W. Scott (Technical Monitor)

2001-01-01

This investigation involved the fabrication and evaluation of rare-earth oxide selective emitters. The first goal of this study was to successfully fabricate the selective emitter samples using paper and ceramic materials processing techniques. The resulting microstructure was also analyzed using a Scanning Electron Microscope. All selective emitter samples fabricated for this study were made with ytterbium oxide (Yb2O3). The second goal of this study involved the measurement of the spectral emission and the radiated power of all the selective emitter samples. The final goal of this study involved the direct comparison of the radiated power emitted by the selective emitter samples to that of a standard blackbody at the same temperature and within the same wavelength range.

Flying across Galaxy Clusters with Google Earth: additional imagery from SDSS co-added data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hao, Jiangang; Annis, James; /Fermilab

2010-10-01

Galaxy clusters are spectacular. We provide a Google Earth compatible imagery for the deep co-added images from the Sloan Digital Sky Survey and make it a tool for examing galaxy clusters. Google Earth (in sky mode) provides a highly interactive environment for visualizing the sky. By encoding the galaxy cluster information into a kml/kmz file, one can use Google Earth as a tool for examining galaxy clusters and fly across them freely. However, the resolution of the images provided by Google Earth is not very high. This is partially because the major imagery google earth used is from Sloan Digitalmore » Sky Survey (SDSS) (SDSS collaboration 2000) and the resolutions have been reduced to speed up the web transferring. To have higher resolution images, you need to add your own images in a way that Google Earth can understand. The SDSS co-added data are the co-addition of {approx}100 scans of images from SDSS stripe 82 (Annis et al. 2010). It provides the deepest images based on SDSS and reach as deep as about redshift 1.0. Based on the co-added images, we created color images in a way as described by Lupton et al. (2004) and convert the color images to Google Earth compatible images using wcs2kml (Brewer et al. 2007). The images are stored at a public server at Fermi National Accelerator Laboratory and can be accessed by the public. To view those images in Google Earth, you need to download a kmz file, which contains the links to the color images, and then open the kmz file with your Google Earth. To meet different needs for resolutions, we provide three kmz files corresponding to low, medium and high resolution images. We recommend the high resolution one as long as you have a broadband Internet connection, though you should choose to download any of them, depending on your own needs and Internet speed. After you open the downloaded kmz file with Google Earth (in sky mode), it takes about 5 minutes (depending on your Internet connection and the resolution of

Hot-pressed silicon nitride with various lanthanide oxides as sintering additives

NASA Technical Reports Server (NTRS)

Ueno, K.; Toibana, Y.

1984-01-01

The effects of addition of various lanthanide oxides and their mixture with Y2O3 on the sintering of Si3N4 were investigated. The addition of simple and mixed lanthanide oxides promoted the densification of Si3N4 in hot-pressing at 1800 C under 300-400kg/ centimeters squared for 60 min. The crystallization of yttrium and lanthanide-silicon oxynitrides which was observed inn the sintered body containing yttrium-lanthanide mixed oxides as additives led to the formation of a highly refractory Si3N4 ceramic having a bending strength of 82 and 84 kg/millimeters squared at room temperature and 1300 C respectively. In a Y2O3+La2O3 system, a higher molar ratio of La2O3 to Y2O3 gave a higher hardness and strength at high temperatures. It was found that 90 min was an optimum sintering time for the highest strength.

Stability and anisotropy of (FexNi1-x)2O under high pressure and implications in Earth's and super-Earths' core.

PubMed

Huang, Shengxuan; Wu, Xiang; Qin, Shan

2018-01-10

Oxygen is thought to be an important light element in Earth's core but the amount of oxygen in Earth's core remains elusive. In addition, iron-rich iron oxides are of great interest and significance in the field of geoscience and condensed matter physics. Here, static calculations based on density functional theory demonstrate that I4/mmm-Fe 2 O is dynamically and mechanically stable and becomes energetically favorable with respect to the assemblage of hcp-Fe and [Formula: see text]-FeO above 270 GPa, which indicates that I4/mmm-Fe 2 O can be a strong candidate phase for stable iron-rich iron oxides at high pressure, perhaps even at high temperature. The elasticity and anisotropy of I4/mmm-(Fe x Ni 1-x ) 2 O at high pressures are also determined. Based on these results, we have derived the upper limit of oxygen to be 4.3 wt% in Earth's lower outer core. On the other hand, I4/mmm-(Fe x Ni 1-x ) 2 O with high AV S is likely to exist in a super-Earth's or an ocean planet's solid core causing the locally seismic heterogeneity. Our results not only give some clues to explore and synthesize novel iron-rich iron oxides but also shed light on the fundamental information of oxygen in the planetary core.

Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

DOEpatents

Poston, J.A.

1997-12-02

Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

DOEpatents

Poston, James A.

1997-01-01

Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

Effects of rare earth oxide nanoparticles on root elongation of plants.

PubMed

Ma, Yuhui; Kuang, Linglin; He, Xiao; Bai, Wei; Ding, Yayun; Zhang, Zhiyong; Zhao, Yuliang; Chai, Zhifang

2010-01-01

The phytotoxicity of four rare earth oxide nanoparticles, nano-CeO(2), nano-La(2)O(3), nano-Gd(2)O(3) and nano-Yb(2)O(3) on seven higher plant species (radish, rape, tomato, lettuce, wheat, cabbage, and cucumber) were investigated in the present study by means of root elongation experiments. Their effects on root growth varied greatly between different nanoparticles and plant species. A suspension of 2000 mg L(-1) nano-CeO(2) had no effect on the root elongation of six plants, except lettuce. On the contrary, 2000 mg L(-1) suspensions of nano-La(2)O(3), nano-Gd(2)O(3) and nano-Yb(2)O(3) severely inhibited the root elongation of all the seven species. Inhibitory effects of nano-La(2)O(3), nano-Gd(2)O(3), and nano-Yb(2)O(3) also differed in the different growth process of plants. For wheat, the inhibition mainly took place during the seed incubation process, while lettuce and rape were inhibited on both seed soaking and incubation process. The fifty percent inhibitory concentrations (IC(50)) for rape were about 40 mg L(-1) of nano-La(2)O(3), 20mg L(-1) of nano-Gd(2)O(3), and 70 mg L(-1) of nano-Yb(2)O(3), respectively. In the concentration ranges used in this study, the RE(3+) ion released from the nanoparticles had negligible effects on the root elongation. These results are helpful in understanding phytotoxicity of rare earth oxide nanoparticles. Copyright 2009 Elsevier Ltd. All rights reserved.

Effects of Graphene Oxide Addition on Mechanical and Thermal Properties of Evoh Films

NASA Astrophysics Data System (ADS)

González-Ruiz, Jesús; Yataco-Lazaro, Lourde; Virginio, Sueli; das Graças da Silva-Valenzuela, Maria; Moura, Esperidiana; Valenzuela-Díaz, Francisco

Currently, ethylene vinyl alcohol (EVOH) is one of the oxygen barrier materials most used for food packaging. The addition of graphene oxide nanosheets to the EVOH matrix is employed to improve their mechanic al and barrier properties. In this work, films of EVOH-based composites reinforced with graphene oxide were prepared by melt extrusion, using a twin screw extruder machine and blown extrusion process. The graphene oxide was prepared via chemical oxidation of natural graphite and then was exfoliated into nanosheets using the sonochemical method. The composite films samples were characterized using FTIR and DSC analysis. In addition, their mechanical properties were also determined.

Rare-Earth Oxide Ion (Tm3+, Ho3+, and U3+) Doped Glasses and Fibres for 1.8 to 4 Micrometer Coherent and Broadband Sources

DTIC Science & Technology

2006-07-24

oxide ( TeO2 ) , fluorine- containing silicate (SiOF2) and germanate (GeOF2) glass hosts for each dopant by characterising the spectroscopic properties...Earth Oxide Ion (Tm3+, Ho3+, And U3+) Doped Glasses And Fibres For 1.8 To 4 Micrometer Coherent And Broadband Sources 5c. PROGRAM ELEMENT NUMBER 5d...Rare-earth oxide ion (Tm3+, Ho3+, and U3+) doped glasses and fibres for 1.8 to 4 micrometer coherent and broadband sources Report prepared

Unraveling Recrystallization Mechanisms Governing Texture Development from Rare Earth Element Additions to Magnesium

NASA Astrophysics Data System (ADS)

Imandoust, Aidin

The origin of texture components associated with rare-earth (RE) element additions in wrought magnesium (Mg) alloys is a long-standing problem in magnesium technology. The objective of this research is to identify the mechanisms accountable for rare-earth texture during dynamic recrystallization (DRX). Towards this end, we designed binary Mg-Cerium and Mg-Gadolinium alloys along with complex alloy compositions containing zinc, yttrium and Mischmetal. Binary alloys along with pure Mg were designed to individually investigate their effects on texture evolutions, while complex compositions are designed to develop randomized texture, and be used in automotive and aerospace applications. We selected indirect extrusion to thermo-mechanically process our materials. Different extrusion ratios and speeds were designed to produce partially and fully recrystallized microstructures, allowing us to analyze DRX from its early stages to completion. X-ray diffraction, electron backscattered diffraction (EBSD) and transmission electron microscopy (TEM) were used to conduct microstructure and texture analyses. Our analyses revealed that rare-earth elements in zinc-containing magnesium alloys promote discontinuous dynamic recrystallization at the grain boundaries. During nucleation, the effect of rare earth elements on orientation selection was explained by the concomitant actions of multiple Taylor axes in the same grain. Isotropic grain growth was observed due to rare earth elements segregating to grain boundaries, which lead to texture randomization. The nucleation in binary Mg-RE alloys took place by continuous formation of necklace structures. Stochastic relaxation of basal and non-basal dislocations into low-angle grain boundaries produced chains of embryos with nearly random orientations. Schmid factor analysis showed a lower net activation of dislocations in RE textured grains compared to ones on the other side of the stereographic triangle. Lower dislocation densities within

Process for depositing epitaxial alkaline earth oxide onto a substrate and structures prepared with the process

DOEpatents

McKee, Rodney A.; Walker, Frederick J.

1996-01-01

A process and structure involving a silicon substrate utilize molecular beam epitaxy (MBE) and/or electron beam evaporation methods and an ultra-high vacuum facility to grow a layup of epitaxial alkaline earth oxide films upon the substrate surface. By selecting metal constituents for the oxides and in the appropriate proportions so that the lattice parameter of each oxide grown closely approximates that of the substrate or base layer upon which oxide is grown, lattice strain at the film/film or film/substrate interface of adjacent films is appreciably reduced or relieved. Moreover, by selecting constituents for the oxides so that the lattice parameters of the materials of adjacent oxide films either increase or decrease in size from one parameter to another parameter, a graded layup of films can be grown (with reduced strain levels therebetween) so that the outer film has a lattice parameter which closely approximates that of, and thus accomodates the epitaxial growth of, a pervoskite chosen to be grown upon the outer film.

Oxidation and protection of fiberglass-epoxy composite masts for photovoltaic arrays in the low earth orbital environment

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Ciancone, Michael L.; Paulsen, Phillip E.; Brady, Joyce A.

1988-01-01

The extent of degradation of fiberglass-epoxy composite masts of the Space Station solar array panel, when these are exposed to atomic oxygen environment of the low-earth orbit, was investigated in ground testing of fiberglass-epoxy composites in an RF plasma asher. In addition, several methods of protecting the composite structures were evaluated, including an aluminum braid covering, an In-Sn eutectic, and a silicone based paint. It was found that, during exposure, the epoxy at the surface of the composite was oxidized, exposing individual glass fibers which could easily be removed. The results of mass measurements and SEM examination carried out after thermal cycling and flexing of exposed composite samples indicated that coatings such as In-Sn eutectic may provide adequate protection by containing the glass fibers, even though mass loss still occurs.

Defect Clustering and Nano-phase Structure Characterization of Multicomponent Rare Earth-Oxide-Doped Zirconia-Yttria Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

2004-01-01

Advanced thermal barrier coatings (TBCs) have been developed by incorporating multicomponent rare earth oxide dopants into zirconia-based thermal barrier coatings to promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nanophases within the coating systems. In this paper, the defect clusters, induced by Nd, Gd, and Yb rare earth dopants in the zirconia-yttria thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The TEM lattice imaging, selected area diffraction (SAD), and electron energy-loss spectroscopy (EELS) analyses demonstrated that the extensive nanoscale rare earth dopant segregation exists in the plasma-sprayed and electron-physical-vapor-deposited (EB PVD) thermal barrier coatings. The nanoscale concentration heterogeneity and the resulting large lattice distortion promoted the formation of parallel and rotational defective lattice clusters in the coating systems. The presence of the 5-to 100-nm-sized defect clusters and nanophases is believed to be responsible for the significant reduction of thermal conductivity, improved sintering resistance, and long-term high temperature stability of the advanced thermal barrier coating systems.

Determination of thorium and of rare earth elements in cerium earth minerals and ores

USGS Publications Warehouse

Carron, M.K.; Skinner, D.L.; Stevens, R.E.

1955-01-01

The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

X-ray Diffraction Studies of the Structure and Thermochemistry of Alkaline-Earth Oxide-Coated Thermionic Cathodes

NASA Technical Reports Server (NTRS)

Karikari, E. K.; Bassey, E.; Wintucky, Edwin G.

1998-01-01

NASA LeRC has a broad, active cathode technology development program in which both experimental and theoretical studies are being employed to further development of thermionic cathodes for use as electron sources in vacuum devices for communications and other space applications. One important type of thermionic cathode under development is the alkaline-earth oxide-coated (BaO, SrO, CaO) cathode. Significant improvements in the emission characteristics of this cathode have been obtained through modification of the chemical composition and morphology of the oxide coating, with the best result thus far coming from the addition of In2O3 and Sc2O3. Whereas the In2O3 produces a finer, more uniform particle structure, the exact chemical state and role of the Sc2O3 in the emission enhancement is unknown. The purpose of this cooperative agreement is to combine the studies of the surface chemistry and electron emission at NASA LeRC of chemically modified oxide coatings with a study of the thermochemistry and crystal structure using X-ray diffraction equipment and expertise at Clark Atlanta University (CAU). The study at CAU is intended to provide the description and understanding of the structure and thermochemistry needed for further improvement and optimization of the modified coatings. A description of the experimental procedure, preliminary X-ray diffraction test results, together with the design of an ultrahigh vacuum chamber necessary for high temperature thermochemistry studies will be presented.

Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Hansel, C. M.; Wankel, S. D.

2015-12-01

Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

Single Crystal Fibers of Yttria-Stabilized Cubic Zirconia with Ternary Oxide Additions

NASA Technical Reports Server (NTRS)

Ritzert, F. J.; Yun, H. M.; Miner, R. V.

1997-01-01

Single crystal fibers of yttria (Y2O3)-stabilized cubic zirconia, (ZrO2) with ternary oxide additions were grown using the laser float zone fiber processing technique. Ternary additions to the ZrO2-Y2O3 binary system were studied aimed at increasing strength while maintaining the high coefficient of thermal expansion of the binary system. Statistical methods aided in identifying the most promising ternary oxide candidate (Ta2O5, Sc2O3, and HfO2) and optimum composition. The yttria, range investigated was 14 to 24 mol % and the ternary oxide component ranged from 1 to 5 mol %. Hafnium oxide was the most promising ternary oxide component based on 816 C tensile strength results and ease of fabrication. The optimum composition for development was 81 ZrO2-14 Y203-5 HfO2 based upon the same elevated temperature strength tests. Preliminary results indicate process improvements could improve the fiber performance. We also investigated the effect of crystal orientation on strength.

Fe-oxide mineralogy of the Jiujiang red earth sediments and implications for Quaternary climate change, southern China.

PubMed

Yin, Ke; Hong, Hanlie; Algeo, Thomas J; Churchman, Gordon Jock; Li, Zhaohui; Zhu, Zongmin; Fang, Qian; Zhao, Lulu; Wang, Chaowen; Ji, Kaipeng; Lei, Weidong; Duan, Zhenggang

2018-02-26

Diffuse reflectance spectrophotometry (DRS) is a new, fast, and reliable method to characterize Fe-oxides in soils. The Fe-oxide mineralogy of the Jiujiang red earth sediments was investigated using DRS to investigate the climate evolution of southern China since the mid-Pleistocene. The DRS results show that hematite/(hematite + goethite) ratios [Hm/(Hm + Gt)] exhibit an upward decreasing trend within the Jiujiang section, suggesting a gradual climate change from warm and humid in the middle Pleistocene to cooler and drier in the late Pleistocene. Upsection trends toward higher (orthoclase + plagioclase)/quartz ratios [(Or + Pl)/Q] and magnetic susceptibility values (χ lf ) support this inference, which accords with global climate trends at that time. However, higher-frequency climatic subcycles observed in loess sections of northern China are not evident in the Jiujiang records, indicating a relatively lower climate sensitivity of the red earth sediments in southern China.

Wide-band-gap, alkaline-earth-oxide semiconductor and devices utilizing same

DOEpatents

Abraham, Marvin M.; Chen, Yok; Kernohan, Robert H.

1981-01-01

This invention relates to novel and comparatively inexpensive semiconductor devices utilizing semiconducting alkaline-earth-oxide crystals doped with alkali metal. The semiconducting crystals are produced by a simple and relatively inexpensive process. As a specific example, a high-purity lithium-doped MgO crystal is grown by conventional techniques. The crystal then is heated in an oxygen-containing atmosphere to form many [Li].degree. defects therein, and the resulting defect-rich hot crystal is promptly quenched to render the defects stable at room temperature and temperatures well above the same. Quenching can be effected conveniently by contacting the hot crystal with room-temperature air.

Robust Hydrophobic Surfaces from Suspension HVOF Thermal Sprayed Rare-Earth Oxide Ceramics Coatings.

PubMed

Bai, M; Kazi, H; Zhang, X; Liu, J; Hussain, T

2018-05-03

This study has presented an efficient coating method, namely suspension high velocity oxy-fuel (SHVOF) thermal spraying, to produce large super-hydrophobic ceramic surfaces with a unique micro- and nano-scale hierarchical structures to mimic natural super-hydrophobic surfaces. CeO 2 was selected as coatings material, one of a group of rare-earth oxide (REO) ceramics that have recently been found to exhibit intrinsic hydrophobicity, even after exposure to high temperatures and abrasive wear. Robust hydrophobic REO ceramic surfaces were obtained from the deposition of thin CeO 2 coatings (3-5 μm) using an aqueous suspension with a solid concentration of 30 wt.% sub-micron CeO 2 particles (50-200 nm) on a selection of metallic substrates. It was found that the coatings' hydrophobicity, microstructure, surface morphology, and deposition efficiency were all determined by the metallic substrates underneath. More importantly, it was demonstrated that the near super-hydrophobicity of SHVOF sprayed CeO 2 coatings was achieved not only by the intrinsic hydrophobicity of REO but also their unique hierarchically structure. In addition, the coatings' surface hydrophobicity was sensitive to the O/Ce ratio, which could explain the 'delayed' hydrophobicity of REO coatings.

Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway.

PubMed

Su, Guijin; Liu, Yexuan; Huang, Linyan; Shi, Yali; Zhang, Aiqian; Zhang, Lixia; Liu, Wenbin; Gao, Lirong; Zheng, Minghui

2013-01-01

The degradation of hexachlorobenzene (HCB) was carried out over physical mixtures of a series of alkaline earth metal oxides (MO: M=Mg, Ca, Sr, Ba) and iron oxides with different crystal types (Fe(x)O(y):Fe(2)O(3) or Fe(3)O(4)) at 300°C. These physical mixtures all showed a synergetic effect toward the degradation of HCB. A range of degradation products were identified by various methods, including tri- to penta-chlorobenzenes by gas chromatography/mass spectrometry (GC-MS), tri- to penta-chlorophenols, tetrachlorocatechol (TCC) and tetrachlorohydroquinone (TCHQ) by GC-MS after derivatization, and formic and acetic acids by ion chromatography. Two degradation pathways, hydrodechlorination and oxidative degradation, appear to occur competitively. However, more sequential chlorinated benzene and phenol congeners were formed over mixed MO/Fe(3)O(4) than over mixed MO/Fe(2)O(3) under the same conditions. The oxidative reaction dominated over mixed MO/Fe(2)O(3) and was promoted as the major reaction by the synergetic effect, while both the oxidative and hydrodechlorination reactions were important over mixed MO/Fe(3)O(4), and both pathways are remarkably promoted by the synergetic effect. The enhanced hydrodechlorination may be attributed to free electrons generated by the transformation of Fe(3)O(4) into Fe(2)O(3), and hydrogen provided by water adsorbed on the MO. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of oxide additions and temperature on sinterability of milled silicon nitride

NASA Technical Reports Server (NTRS)

Arias, A.

1980-01-01

Specimens of milled alpha-Si3N4 with 0 to 5.07 equivalent percent of oxide additions were pressureless sintered at 1650 to 1820 C for 4 hours in nitrogen while covered with powdered Si3N4 + SiO2. Densities of less than or equal to 97.5 percent resulted with approximately 2.5 equivalent percent of MgO, CeO2, Y2O3, and three mixtures involving these oxides. Densities of greater than or equal to 94 percent were obtained with approximately 0.62 equivalent percent of the same additives. At most temperatures, best sinterability (density maxima) was obtained with 1.2 to 2.5 equivalent percent additive.

Effect of the introduction of oxide ion vacancies into cubic fluorite-type rare earth oxides on the NO decomposition catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masui, Toshiyuki; Nagai, Ryosuke; Imanaka, Nobuhito, E-mail: imanaka@chem.eng.osaka-u.ac.jp

2014-12-15

Cubic fluorite-type solid solutions based on Pr{sub 6}O{sub 11} and CeO{sub 2} were synthesized and oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice through the charge compensating mechanism by Mg{sup 2+} and/or Ca{sup 2+} doping into their lattices. The oxide anion vacancies bring about positive effect on NO decomposition catalysis. The reason for the increase in the catalytic activity was attributed to defect fluorite-type structures close to the C-type cubic one, because C-type cubic rare earth oxides, in which one-quarter of the oxygen atoms in the fluorite-type structure are removed, show high NO decomposition activity. In particular,more » the positive effect of the formation of oxide anion vacancies was significant for Pr{sub 6}O{sub 11} and its solid solutions, because the molar volume of Pr{sub 6}O{sub 11} is larger than that of CeO{sub 2}, and Pr{sub 6}O{sub 11} contains Pr{sup 3+} as well as Pr{sup 4+} and thereby a small amount of oxide anion vacancies exist inherently in the lattice. - Graphical abstract: Oxide anion vacancies intentionally introduced into the cubic fluorite-type lattice bring about positive effect on NO decomposition catalysis. - Highlights: • Cubic fluorite-type solid solutions were synthesized. • Oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice. • The oxide anion vacancies bring about positive effect on NO decomposition catalysis. • The activity was enhanced by making the structure close to the C-type cubic one.« less

Luminescence studies of rare earth doped yttrium gadolinium mixed oxide phosphor

NASA Astrophysics Data System (ADS)

Som, S.; Choubey, A.; Sharma, S. K.

2012-09-01

This paper reports the photoluminescence and thermoluminescence properties of gamma ray induced rare earth doped yttrium gadolinium mixed oxide phosphor. The europium (Eu3+) was used as rare earth dopant. The phosphor was prepared by chemical co-precipitation method according to the formula (Y2-x-yGdx) O3: Euy3+ (x=0.5; y=0.05). The photoluminescence emission spectrum of the prepared phosphor shows intense peaks in the red region at 615 nm for 5D0→7F2 transitions and the photoluminescence excitation spectra show a broad band located around 220-270 nm for the emission wavelength fixed at 615 nm. The thermoluminescence studies were carried out after irradiating the phosphor by gamma rays in the dose range from 100 Gy to 1 KGy. In the thermoluminescence glow curves, one single peak was observed at about 300 °C of which the intensity increases linearly in the studied dose range of gamma rays. The glow peak was deconvoluted by GlowFit program and the kinetic parameters associated with the deconvoluted peaks were calculated. The kinetic parameters were also calculated by various glow curve shape and heating rate methods.

Effect of Alloying Additions on Oxidation Behaviors of Ni-Fe Based Superalloy for Ultra-Supercritical Boiler Applications

NASA Astrophysics Data System (ADS)

Lu, Jintao; Yang, Zhen; Zhao, Xinbao; Yan, Jingbo; Gu, Y.

A new kind of Ni-Fe-based superalloy is designed recently for 750 °C-class A-USC boiler tube. The oxidation behavior of the designed alloys with various combinations of anti-oxidation additions, Cr, Al and Si, was investigated at 750 °C and 850 °C, respectively. The results indicated that the oxidation rate of tested alloys decreased with the increase of the sum of additions. Cr addition may drop the relative constant of parabolic rate greatly when temperature is raised. But the oxide scale, mainly consisted of NiCr spinel at 750 °C and NiCrMn spinel at 850 °C, was similar while the Cr content is in a range of 20-25 wt.% at tested temperatures. Al addition, however, showed the best effective to reduce the oxidation rates. Internal Al-rich oxide was observed at the scale/metal interface for alloys added with high content of Al and was increased with Al content increase. Very tiny difference between the oxide scales of the Si-added alloys was identified when Si content varies among 0.02-0.05 wt.%. Basing on these results, this presentation discussed the optimum combination of anti-oxidation additions as well as oxidation mechanisms in the designed Ni-Fe-base superalloy.

Water addition regulates the metabolic activity of ammonia oxidizers responding to environmental perturbations in dry subhumid ecosystems.

PubMed

Hu, Hang-Wei; Macdonald, Catriona A; Trivedi, Pankaj; Holmes, Bronwyn; Bodrossy, Levente; He, Ji-Zheng; Singh, Brajesh K

2015-02-01

Terrestrial arid and semi-arid ecosystems (drylands) constitute about 41% of the Earth's land surface and are predicted to experience increasing fluctuations in water and nitrogen availability. Mounting evidence has confirmed the significant importance of ammonia-oxidizing archaea (AOA) and bacteria (AOB) in nitrification, plant nitrogen availability and atmospheric N2 O emissions, but their responses to environmental perturbations in drylands remain largely unknown. Here we evaluate how the factorial combinations of irrigation and fertilization in forests and land-use change from grassland to forest affects the dynamics of AOA and AOB following a 6-year dryland field study. Potential nitrification rates and AOA and AOB abundances were significantly higher in the irrigated plots, accompanied by considerable changes in community compositions, but their responses to fertilization alone were not significant. DNA-stable isotope probing results showed increased (13) CO2 incorporation into the amoA gene of AOA, but not of AOB, in plots receiving water addition, coupled with significantly higher net mineralization and nitrification rates. High-throughput microarray analysis revealed that active AOA assemblages belonging to Nitrosopumilus and Nitrosotalea were increasingly labelled by (13) CO2 following irrigation. However, no obvious effects of land-use changes on nitrification rates or metabolic activity of AOA and AOB could be observed under dry conditions. We provide evidence that water addition had more important roles than nitrogen fertilization in influencing the autotrophic nitrification in dryland ecosystems, and AOA are increasingly involved in ammonia oxidation when dry soils become wetted. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

Ab initio calculations on the positive ions of the alkaline-earth oxides, fluorides, and hydroxides

NASA Technical Reports Server (NTRS)

Partridge, H.; Langhoff, S. R.; Bauschlicher, C. W., Jr.

1986-01-01

Theoretical dissociation energies are presented for the alkaline-earth fluoride, hydroxide, and oxide positive ions that are considered to be accurate to 0.1-0.2 eV. The r(e) for the positive ions are found to be consistently shorter than the corresponding neutrals by 0.07 + or -0.02 A. The bonding in the ground states is demonstrated to be of predominantly M + 2 X - character. The a 3 Pi and A 1 Pi are found to lie considerably above the X 1 Sigma + ground states of the alkaline-earth fluoride and hydroxide positive ions. The overall agreement of the theoretical ionization potentials with the available experimental appearance potentials is satisfactory; these values should represent the most accurate and consistent set available.

The effect of aluminum additions on the oxidation resistance of U 3Si 2

DOE PAGES

Wood, E. Sooby; White, J. T.; Nelson, A. T.

2017-04-01

The effect of aluminum additions to U 3Si 2 is investigated in this paper as a means to improve the oxidation resistance of this nuclear fuel form. Four U-Si-Al compositions have been synthesized and characterized using scanning electron microscopy, energy dispersive spectroscopy, and x-ray diffraction. The onsets of breakaway oxidation are identified in air thermal ramp tests using thermogravimetric analysis. The final oxidation products following 1000° C air exposure are identified using x-ray diffraction and compared to those of UO 2 and U metal oxidized in the same manner. Finally, thermogravimetric data acquired in this study indicates that increasing amountsmore » of Al in U 3Si 2 further delays the onset of breakaway oxidation, providing enhanced oxidation resistance in air. Al 2O 3 formation on U 3Al 2Si 3 is observed following a heat treatment performed at 500° C in air, demonstrating the potential of Al additions to improve the oxidation resistance of U 3Si 2.« less

The effect of aluminum additions on the oxidation resistance of U 3Si 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wood, E. Sooby; White, J. T.; Nelson, A. T.

The effect of aluminum additions to U 3Si 2 is investigated in this paper as a means to improve the oxidation resistance of this nuclear fuel form. Four U-Si-Al compositions have been synthesized and characterized using scanning electron microscopy, energy dispersive spectroscopy, and x-ray diffraction. The onsets of breakaway oxidation are identified in air thermal ramp tests using thermogravimetric analysis. The final oxidation products following 1000° C air exposure are identified using x-ray diffraction and compared to those of UO 2 and U metal oxidized in the same manner. Finally, thermogravimetric data acquired in this study indicates that increasing amountsmore » of Al in U 3Si 2 further delays the onset of breakaway oxidation, providing enhanced oxidation resistance in air. Al 2O 3 formation on U 3Al 2Si 3 is observed following a heat treatment performed at 500° C in air, demonstrating the potential of Al additions to improve the oxidation resistance of U 3Si 2.« less

The Effect of Low Earth Orbit Atomic Oxygen Exposure on Phenylphosphine Oxide-Containing Polymers

NASA Technical Reports Server (NTRS)

Connell, John W.

2000-01-01

Thin films of phenylphosphine oxide-containing polymers were exposed to low Earth orbit aboard a space shuttle flight (STS-85) as part of flight experiment designated Evaluation of Space Environment and Effects on Materials (ESEM). This flight experiment was a cooperative effort between the NASA Langley Research Center (LaRC) and the National Space Development Agency of Japan (NASDA). The thin film samples described herein were part of an atomic oxygen exposure experiment (AOE) and were exposed to primarily atomic oxygen (1 X 1019 atoms/cm2). The thin film samples consisted of three phosphine oxide containing polymers (arylene ether, benzimidazole and imide). Based on post-flight analyses using atomic force microscopy, X-ray photoelectron spectroscopy, and weight loss data, it was found that atomic oxygen exposure of these materials efficiently produces a phosphate layer at the surface of the samples. This layer provides a barrier towards further attack by AO. Consequently, these materials do not exhibit linear erosion rates which is in contrast with most organic polymers. Qualitatively, the results obtained from these analyses compare favorably with those obtained from samples exposed to atomic oxygen and or oxygen plasma in ground based exposure experiments. The results of the low Earth orbit atomic oxygen exposure on these materials will be compared with those of ground based exposure to AO.

Transformation of Cerium Oxide Nanoparticles from a Diesel Fuel Additive during Combustion in a Diesel Engine.

PubMed

Dale, James G; Cox, Steven S; Vance, Marina E; Marr, Linsey C; Hochella, Michael F

2017-02-21

Nanoscale cerium oxide is used as a diesel fuel additive to reduce particulate matter emissions and increase fuel economy, but its fate in the environment has not been established. Cerium oxide released as a result of the combustion of diesel fuel containing the additive Envirox, which utilizes suspended nanoscale cerium oxide to reduce particulate matter emissions and increase fuel economy, was captured from the exhaust stream of a diesel engine and was characterized using a combination of bulk analytical techniques and high resolution transmission electron microscopy. The combustion process induced significant changes in the size and morphology of the particles; ∼15 nm aggregates consisting of 5-7 nm faceted crystals in the fuel additive became 50-300 nm, near-spherical, single crystals in the exhaust. Electron diffraction identified the original cerium oxide particles as cerium(IV) oxide (CeO 2 , standard FCC structure) with no detectable quantities of Ce(III), whereas in the exhaust the ceria particles had additional electron diffraction reflections indicative of a CeO 2 superstructure containing ordered oxygen vacancies. The surfactant coating present on the cerium oxide particles in the additive was lost during combustion, but in roughly 30% of the observed particles in the exhaust, a new surface coating formed, approximately 2-5 nm thick. The results of this study suggest that pristine, laboratory-produced, nanoscale cerium oxide is not a good substitute for the cerium oxide released from fuel-borne catalyst applications and that future toxicity experiments and modeling will require the use/consideration of more realistic materials.

Hydrothermal method of synthesis of rare-earth tantalates and niobates

DOEpatents

Nyman, May D; Rohwer, Lauren E.S.; Martin, James E

2012-10-16

A hydrothermal method of synthesis of a family of rare-earth Group 5 oxides, where the Group 5 oxide is a niobate or tantalate. The rare-earth Group 5 oxides can be doped with suitable emitter ions to form nanophosphors.

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

DOE PAGES

Evans, William J.

2016-09-15

A fundamental aspect of any element is the range of oxidation states accessible for useful chemistry. This tutorial describes the recent expansion of the number of oxidation states available to the rare-earth and actinide metals in molecular complexes that has resulted through organometallic chemistry involving the cyclopentadienyl ligand. These discoveries demonstrate that the cyclopentadienyl ligand, which has been a key component in the development of organometallic chemistry since the seminal discovery of ferrocene in the 1950s, continues to contribute to the advancement of science. Lastly, we present background information on the rare-earth and actinide elements, as well as the sequencemore » of events that led to these unexpected developments in the oxidation state chemistry of these metals.« less

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, William J.

A fundamental aspect of any element is the range of oxidation states accessible for useful chemistry. This tutorial describes the recent expansion of the number of oxidation states available to the rare-earth and actinide metals in molecular complexes that has resulted through organometallic chemistry involving the cyclopentadienyl ligand. These discoveries demonstrate that the cyclopentadienyl ligand, which has been a key component in the development of organometallic chemistry since the seminal discovery of ferrocene in the 1950s, continues to contribute to the advancement of science. Lastly, we present background information on the rare-earth and actinide elements, as well as the sequencemore » of events that led to these unexpected developments in the oxidation state chemistry of these metals.« less

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

NASA Astrophysics Data System (ADS)

Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

2017-03-01

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

Formation of H a - hydrogen centers upon additive coloration of alkaline-earth fluoride crystals

NASA Astrophysics Data System (ADS)

Radzhabov, E. A.; Egranov, A. V.; Shendrik, R. Yu.

2017-06-01

The mechanism of coloration of alkaline-earth fluoride crystals CaF2, SrF2, and BaF2 in calcium vapors in an autoclave with a cold zone is studied. It was found that the pressure in the autoclave upon constant evacuation by a vacuum pump within the temperature range of 500-800°C increases due to evaporation of metal calcium. In addition to the optical-absorption bands of color centers in the additively colored undoped crystals or to the bands of divalent ions in the crystals doped with rare-earth Sm, Yb, and Tm elements, there appear intense bands in the vacuum ultraviolet region at 7.7, 7.0, and 6.025 eV in CaF2, SrF2, and BaF2, respectively. These bands belong to the Ha - hydrogen centers. The formation of hydrogen centers is also confirmed by the appearance of the EPR signal of interstitial hydrogen atoms after X-ray irradiation of the additively colored crystals. Grinding of the outer edges of the colored crystals leads to a decrease in the hydrogen absorption-band intensity with depth to complete disappearance. The rate of hydrogen penetration inside the crystal is lower than the corresponding rate of color centers (anion vacancies) by a factor of tens. The visible color density of the outer regions of the hydrogen-containing crystals is several times lower than that of the inner region due to the competition between the color centers and hydrogen centers.

Slip casting and extruding shapes of rhenium with metal oxide additives. 1: Feasibility demonstration

NASA Technical Reports Server (NTRS)

Barr, F. A.; Page, R. J.

1986-01-01

The feasibility of fabricating small rhenium parts with metal oxide additives by means of slip casting and extrusion techniques is described. The metal oxides, ZrO2 and HfO2 were stabilized into the cubic phase with Y2O3. Additions of metal oxide to the rhenium of up to 15 weight percent were used. Tubes of 17 mm diameter with 0.5 mm walls were slip cast by adapting current ceramic oxide techniques. A complete cast double conical nozzle demonstrated the ability to meet shapes and tolerances. Extrusion of meter long tubing lengths of 3.9 mm o.d. x 2.3 mm i.d. final dimension is documented. Sintering schedules are presented to produce better than 95% of theoretical density parts. Finished machining was found possible were requried by electric discharge machining and diamond grinding.

Rare Earth Garnet Selective Emitter

NASA Technical Reports Server (NTRS)

Lowe, Roland A.; Chubb, Donald L.; Farmer, Serene C.; Good, Brian S.

1994-01-01

Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approx. = 0.75, sup 4)|(sub 15/2) - (sup 4)|(sub 13/2),for Er-YAG and epsilon(sub lambda) approx. = 0.65, (sup 5)|(sub 7) - (sup 5)|(sub 8) for Ho-YAG) at 1500 K. In addition, low out-of-band spectral emittance, epsilon(sub lambda) less than 0.2, suggest these materials would be excellent candidates for high efficiency selective emitters in thermophotovoltaic (TPV) systems operating at moderate temperatures (1200-1500 K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. Selective emitters in the near IR are of special interest for thermophotovoltaic (TPV) energy conversion. The most promising solid selective emitters for use in a TPV system are rare earth oxides. Early spectral emittance work on rare earth oxides showed strong emission bands in the infrared (0.9 - 3 microns). However, the emittance outside the emission band was also significant and the efficiency of these emitters was low. Recent improvements in efficiency have been made with emitters fabricated from fine (5 - 10 microns) rare earth oxide fibers similar to the Welsbach mantle used in gas lanterns. However, the rare earth garnet emitters are more rugged than the mantle type emitters. A thin film selective emitter on a low emissivity substrate such as gold, platinum etc., is rugged and easily adapted to a wide variety of thermal sources. The garnet structure and its many subgroups have been successfully used as hosts for rare earth ions, introduced as substitutional

Microstructural characterisation of Al-Si cast alloys containing rare earth additions

NASA Astrophysics Data System (ADS)

Elgallad, E. M.; Ibrahim, M. F.; Doty, H. W.; Samuel, F. H.

2018-05-01

This paper presents a thorough study on the effect of rare earth elements, specifically La and Ce, on the microstructure characteristics of non-modified and Sr-modified A356 and A413 alloys. Several alloys were prepared by adding 1% La and 1% Ce either individually or in combination. Microstructural characterisation was carried out using optical microscopy, scanning electron microscopy and electron probe microanalysis as well as differential scanning calorimetry (DSC) analysis. The results showed that the individual and combined additions of La and Ce did not bring about any modification or even refinement in the eutectic Si structure. Moreover, these additions were found to negate the modification effect of Sr, particularly in the presence of La. The A356 and A413 alloys containing La and/or Ce displayed high phase volume fractions owing to the formation of Al-Si-La/Ce/(La,Ce) and Al-Ti-La/Ce intermetallic phases. DSC analysis revealed that the formation temperatures of these phases varied from 560 to 568 °C and 568 to 574 °C, respectively. This analysis also showed that the addition of La and Ce whether individually or in combination resulted in a depression in the eutectic temperature and a considerable increase in the solidification range, particularly for the A413 alloy.

Study of the oxidized and non- oxidized bitumen modified with additive «Adgezolin» by using electron paramagnetic resonance

NASA Astrophysics Data System (ADS)

Mukhamatdinov, I.; Gafurov, M.; Kemalov, A.; Rodionov, A.; Mamin, G.; Fakhretdinov, P.

2018-05-01

Cationic surfactant (adhesion additive) «Adgezolin» has been developed. It is shown that introduction of «Adgezolin» into the oxidized bitumen increases the relative amount of asphaltenes and monocyclearomatic hydrocarbons. By means of electron paramagnetic resonance (EPR) it is demonstrated that the introduction of additive «Adgezolin» increases the number of paramagnetic «free» carbon radicals (FR) in the oxidized bitumen and decreases that in the unoxidized species. In both types of bitumen shift from the Lorentzian to Gaussian EPR lineshape of FR is obtained that could be connected with as an increase of the samples homogeneity. It is supposed that while in the oxygenated bitumens introduction of additives leads to the disaggregation of asphaltene-resins compounds, in the unoxidized samples the balance is shifted towards formation of di-radicals.

Clouds Composition in Super-Earth Atmospheres: Chemical Equilibrium Calculations

NASA Astrophysics Data System (ADS)

Kempton, Eliza M.-R.; Mbarek, Rostom

2015-12-01

Attempts to determine the composition of super-Earth atmospheres have so far been plagued by the presence of clouds. Yet the theoretical framework to understand these clouds is still in its infancy. For the super-Earth archetype GJ 1214b, KCl, Na2S, and ZnS have been proposed as condensates that would form under the condition of chemical equilibrium, if the planet’s atmosphere has a bulk composition near solar. Condensation chemistry calculations have not been presented for a wider range of atmospheric bulk composition that is to be expected for super-Earth exoplanets. Here we provide a theoretical context for the formation of super-Earth clouds in atmospheres of varied composition by determining which condensates are likely to form, under the assumption of chemical equilibrium. We model super-Earth atmospheres assuming they are formed by degassing of volatiles from a solid planetary core of chondritic material. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350-3,000 K. Clouds should form along the temperature-pressure boundaries where the condensed species appear in our calculations. The super-Earth atmospheres that we study range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solar and super-solar, thereby spanning a diverse range of atmospheric composition that is appropriate for low-mass exoplanets. Some condensates appear across all of our models. However, the majority of condensed species appear only over specific ranges of H:O and C:O ratios. We find that for GJ 1214b, KCl is the primary cloud-forming condensate at solar composition, in agreement with previous work. However, for oxidizing atmospheres, where H:O is less than unity, K2SO4 clouds form instead. For carbon-rich atmospheres with super-solar C:O ratios, graphite clouds additionally appear. At

Evaluation of the strength and radiopacity of Portland cement with varying additions of bismuth oxide.

PubMed

Saliba, E; Abbassi-Ghadi, S; Vowles, R; Camilleri, J; Hooper, S; Camilleri, J

2009-04-01

To study the effect of addition of various proportions of bismuth oxide on compressive strength and radiopacity of Portland cement. The compressive strength of white Portland cement and cement replaced with 10, 15, 20, 25 and 30% bismuth oxide was evaluated by testing cylinders 6 mm in diameter and 12 mm high. Twelve cylinders were tested for each material under study. The radiopacity of the cements tested was evaluated using an aluminium step-wedge and densitometer. The optical density was compared with the relevant thickness of aluminium (Al). Statistical analysis was performed using Analysis of Variance (ANOVA) with P = 0.05 and Tukey test to perform multiple comparison tests. Various additions of bismuth oxide had no significant effect on the strength of the material when compared with the unmodified Portland cement (P > 0.05). The radiopacity of the cements tested ranged from 2.02 mm Al for Portland cement to 9.79 mm Al for the highest bismuth replacement. Addition of bismuth oxide did not affect the compressive strength of Portland cement. All the bismuth oxide cement mixtures had radio-opacities higher than 3 mm thickness of aluminium.

Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Shigaki, H.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.

[Effect of three kinds of rare earth oxides on chromaticity and mechanical properties of zirconia ceramic].

PubMed

Huang, Hui; Zhang, Fu-qiang; Sun, Jing; Gao, Lian

2006-06-01

To evaluate the colouration of zirconia ceramic by adding three kinds of rare earth oxides. The influence of the pigments concentration on the mechanical properties and the microstructure was also analyzed. Added different concentrations of CeO(2), Er(2)O(3) and Pr(6)O(11) in tetragonal zirconia poly crystals stabilized with 3 mol% yttria (3Y-T2P) powder, compacted at 200 MPa using cold isostatic pressure, and sintered to 1 400 degrees C. The heating rate was 150 degrees C/h and the dwelling time was 2 hours. The chromaticity of sintered bodies was measured with chroma meter. The relative density, hardness, flexure strength and fracture toughness were investigated as well. The phase stability of the colorized and pure zirconia was evaluated by X-ray diffraction (XRD) using an automated diffractometer. The microstructures of the specimens were evaluated by scanning electron microscope (SEM). Several kinds of color achieved by the different pigments praseodym oxide, cerium oxide and erbium oxide were presented in the CIELab system. The a* value increased with the added amount of Er(2)O(3), while b* value rose with the increasing amount of CeO(2) and Pr(6)O(11). However, three pigments failed to decrease L* value and the sintered body appeared too bright. Adding three pigments influenced flexure strength of zirconia ceramic significantly, but had little influence on the hardness and fracture toughness. Microscopy revealed the relationship between the porosity and shapes of grains was correlated to strength of the diphase ceramics. No additional phase could be detected by XRD, except t-ZrO(2) in all colorized samples after sintering at 1 400 degrees C for 120 min. Zirconia ceramic can be colorized by CeO(2), Er(2)O(3), and Pr(6)O(11). Pigments even in a small amount influence the mechanical properties of the colorized zirconia material, which necessitates further investigation.

Cu(II) removal by Anoxybacillus flavithermus-iron oxide composites during the addition of Fe(II)aq

NASA Astrophysics Data System (ADS)

Franzblau, Rachel E.; Daughney, Christopher J.; Swedlund, Peter J.; Weisener, Christopher G.; Moreau, Magali; Johannessen, Bernt; Harmer, Sarah L.

2016-01-01

There is currently poor understanding of metal removal by composites of bacteria and iron oxide minerals, even though they commonly co-occur and are among the most important sorbents in near-surface fluid-rock environments. This study evaluated Cu removal by composites of Anoxybacillus flavithermus and iron oxide over time during the addition, oxidation, and hydrolysis of Fe(II)aq and precipitation of the mineral, in comparison to Cu removal in the two single-sorbent end-member systems. In the absence of iron oxide, Cu removal by A. flavithermus was well described by a previously published surface complexation model, after inclusion of additional reactions describing aqueous complexation by exudate ligands released by the bacteria. In the absence of bacterial cells, Cu removal by iron oxide synthesized in the presence of the bacterial exudate ligands demonstrated the formation of ternary surface complexes. Removal of Cu by the A. flavithermus-iron oxide composites was ca. 20% greater than the prediction based on assumption of additivity in the two end-member systems. This non-additive behavior was attributed to (1) progressive physical blockage of bacterial surface sites by the iron oxide particles, (2) physical blockage of adsorption sites as a result of self-aggregation of the iron oxide particles, and (3) the reduction of Cu(II) to Cu(I) at the bacterial cell surface, as demonstrated by X-ray absorption spectroscopy. The extent of reduction of Cu(II) to Cu(I) was proportional to the concentration of solid phase Fe(II), suggesting that iron oxidation and copper reduction are linked. This study has shown that Cu removal by bacteria-iron oxide composites is greatly affected by redox processes such as Cu(II) reduction on the cell surface both by other bacterial surface ligands and the oxidation of sorbed Fe(II), as well as Fe(II) redox interactions, and aging effects of the mineral (i.e. surface site masking).

Insight into self-discharge of layered lithium-rich oxide cathode in carbonate-based electrolytes with and without additive

NASA Astrophysics Data System (ADS)

Li, Jianhui; Xing, Lidan; Zhang, Liping; Yu, Le; Fan, Weizhen; Xu, Mengqing; Li, Weishan

2016-08-01

Self-discharge behavior of layered lithium-rich oxide as cathode of lithium ion battery in a carbonated-based electrolyte is understood, and a simple boron-containing compound, trimethyl borate (TMB), is used as an electrolyte additive to suppress this self-discharge. It is found that layered lithium-rich oxide charged under 4.8 V in additive-free electrolyte suffers severe self-discharge and TMB is an effective electrolyte additive for self-discharge suppression. Physical characterizations from XRD, SEM, TEM, XPS and ICP-MS demonstrate that the crystal structure of the layered lithium-rich oxide collapses due to the chemical interaction between the charged oxide and electrolyte. When TMB is applied, the structural integrity of the oxide is maintained due to the protective cathode film generated from the preferential oxidation of TMB.

Nitrogen Oxides in Early Earth's Atmosphere as Electron Acceptors for Life's Emergence.

PubMed

Wong, Michael L; Charnay, Benjamin D; Gao, Peter; Yung, Yuk L; Russell, Michael J

2017-10-01

We quantify the amount of nitrogen oxides (NOx) produced through lightning and photochemical processes in the Hadean atmosphere to be available in the Hadean ocean for the emergence of life. Atmospherically generated nitrate (NO 3 - ) and nitrite (NO 2 - ) are the most attractive high-potential electron acceptors for pulling and enabling crucial redox reactions of autotrophic metabolic pathways at submarine alkaline hydrothermal vents. The Hadean atmosphere, dominated by CO 2 and N 2 , will produce nitric oxide (NO) when shocked by lightning. Photochemical reactions involving NO and H 2 O vapor will then produce acids such as HNO, HNO 2 , HNO 3 , and HO 2 NO 2 that rain into the ocean. There, they dissociate into or react to form nitrate and nitrite. We present new calculations based on a novel combination of early-Earth global climate model and photochemical modeling, and we predict the flux of NOx to the Hadean ocean. In our 0.1-, 1-, and 10-bar pCO 2 models, we calculate the NOx delivery to be 2.4 × 10 5 , 6.5 × 10 8 , and 1.9 × 10 8 molecules cm -2 s -1 . After only tens of thousands to tens of millions of years, these NOx fluxes are expected to produce sufficient (micromolar) ocean concentrations of high-potential electron acceptors for the emergence of life. Key Words: Nitrogen oxides-Nitrate-Nitrite-Photochemistry-Lightning-Emergence of life. Astrobiology 17, 975-983.

Easy and General Synthesis of Large-Sized Mesoporous Rare-Earth Oxide Thin Films by 'Micelle Assembly'.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Dai, Pengcheng; Yamauchi, Yusuke

2015-12-01

Large-sized (ca. 40 nm) mesoporous Er2O3 thin films are synthesized by using a triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) as a pore directing agent. Each block makes different contributions and the molar ratio of PVP/Er(3+) is crucial to guide the resultant mesoporous structure. An easy and general method is proposed and used to prepare a series of mesoporous rare-earth oxide (Sm2O3, Dy2O3, Tb2O3, Ho2O3, Yb2O3, and Lu2O3) thin films with potential uses in electronics and optical devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

PubMed

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

2017-12-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

Evolution of Earth-like Extrasolar Planetary Atmospheres: Assessing the Atmospheres and Biospheres of Early Earth Analog Planets with a Coupled Atmosphere Biogeochemical Model.

PubMed

Gebauer, S; Grenfell, J L; Stock, J W; Lehmann, R; Godolt, M; von Paris, P; Rauer, H

2017-01-01

Understanding the evolution of Earth and potentially habitable Earth-like worlds is essential to fathom our origin in the Universe. The search for Earth-like planets in the habitable zone and investigation of their atmospheres with climate and photochemical models is a central focus in exoplanetary science. Taking the evolution of Earth as a reference for Earth-like planets, a central scientific goal is to understand what the interactions were between atmosphere, geology, and biology on early Earth. The Great Oxidation Event in Earth's history was certainly caused by their interplay, but the origin and controlling processes of this occurrence are not well understood, the study of which will require interdisciplinary, coupled models. In this work, we present results from our newly developed Coupled Atmosphere Biogeochemistry model in which atmospheric O 2 concentrations are fixed to values inferred by geological evidence. Applying a unique tool (Pathway Analysis Program), ours is the first quantitative analysis of catalytic cycles that governed O 2 in early Earth's atmosphere near the Great Oxidation Event. Complicated oxidation pathways play a key role in destroying O 2 , whereas in the upper atmosphere, most O 2 is formed abiotically via CO 2 photolysis. The O 2 bistability found by Goldblatt et al. ( 2006 ) is not observed in our calculations likely due to our detailed CH 4 oxidation scheme. We calculate increased CH 4 with increasing O 2 during the Great Oxidation Event. For a given atmospheric surface flux, different atmospheric states are possible; however, the net primary productivity of the biosphere that produces O 2 is unique. Mixing, CH 4 fluxes, ocean solubility, and mantle/crust properties strongly affect net primary productivity and surface O 2 fluxes. Regarding exoplanets, different "states" of O 2 could exist for similar biomass output. Strong geological activity could lead to false negatives for life (since our analysis suggests that reducing gases

Effect of simulated Earth reentry exposure on mechanical properties of several oxide dispersion strengthened and superalloy sheet materials

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1977-01-01

The effects of simulated multiple reentry into the earth's atmosphere on the mechanical properties of several high temperature metallic sheet materials were evaluated. The materials included five tin-gage (nominally 0.025- or 0.037-cm) oxide dispersion strengthened (ODS) alloys and two thin-gage (nominally 0.037-cm) superalloys. Multiple reentry conditions were simulated through cyclic Plasma Arc Tunnel (PAT) exposure. PAT exposure generally consisted of 100 cycles of 600 second duration at 1255, 1366, or 1477 K in a Mach 4.6 airstream with an impact pressure of nominally 800 N/m2. PAT exposure generally produced a uniform oxide scale, oxide pits or intergranular oxidation, Kirkendall porosity, and alloy depletion zones except for the aluminum-containing ODS alloys. Only a uniform oxide scale was formed on the aluminum-containing ODS alloys. PAT exposure did not significantly affect the mechanical properties of the thin-gage (nominally 0.025- or 0.037-cm) alloys evaluated. Thus it appears that the microstructural changes produced by Plasma Arc Tunnel exposure has little influence on mechanical properties.

Trivalent Rare-Earth-Metal Bis(trimethylsilyl)amide Halide Complexes by Targeted Oxidations.

PubMed

Bienfait, André M; Wolf, Benjamin M; Törnroos, Karl W; Anwander, Reiner

2018-05-07

In contrast to previously applied salt metathesis protocols the targeted rare-earth-metal compounds Ln[N(SiMe 3 ) 2 ] 2 (halogenido) were accessed by oxidation of Ln(II) silylamide precursors. Treatment of Sm[N(SiMe 3 ) 3 ] 2 (thf) 2 with 0.5 equiv of C 2 Cl 6 or 0.25 equiv of TeBr 4 in thf and crystallization thereof gave [Sm{N(SiMe 3 ) 2 } 2 (μ-X)(thf)] 2 (X = Cl, Br). A similar reaction/crystallization procedure performed with 0.5 equiv of 1,2-diiodoethane gave monomeric Sm[N(SiMe 3 ) 2 ] 2 I(thf) 2 . Switching to Yb[N(SiMe 3 ) 2 ] 2 (thf) 2 , the aforementioned oxidants generated monomeric five-coordinate complexes Yb[N(SiMe 3 ) 2 ] 2 X(thf) 2 (X = Cl, Br, I). The reaction of Eu[N(SiMe 3 ) 2 ] 2 (thf) 2 with 0.5 equiv of C 2 Cl 6 in thf yielded the separated ion pair [Eu{N(SiMe 3 ) 2 } 3 Cl][(thf) 5 Eu(μ-Cl) 2 Eu(thf) 5 ]. Performing the chlorination in n-hexane led to oxidation followed by rapid disproportionation into EuCl 3 (thf) x and Eu[N(SiMe 3 ) 2 ] 3 . The bromination reaction did not afford crystalline material, while the iodination gave crystals of divalent EuI 2 (thf) 5 . Use of trityl chloride (Ph 3 CCl) as the oxidant in thf accomplished the Eu(III) species [Eu{N(SiMe 3 ) 2 } 2 (μ-Cl)(thf)] 2 . In situ oxidation of putative [Tm{N(SiMe 3 ) 2 } 2 (thf) x ] using 0.5 equiv of C 2 Cl 6 in thf followed by crystallization from n-hexane led to the formation of a mixture of [Tm{N(SiMe 3 ) 2 } 2 (μ-Cl)(thf)] 2 and Tm[N(SiMe 3 ) 2 ] 3 . Switching the oxidant to 0.5 equiv of 1,2-diiodoethane and crystallizing from thf repeatedly afforded the bis-halogenated complex Tm[N(SiMe 3 ) 2 ]I 2 (thf) 3 .

Catalytic processes in the atmospheres of earth and Venus

NASA Technical Reports Server (NTRS)

Demore, W. B.; Yung, Y. L.

1982-01-01

Photochemical processes in planetary atmospheres are strongly influenced by catalytic effects of minor constituents. Catalytic cycles in the atmospheres of Earth and Venus are closely related. For example, chlorine oxides (ClOx) act as catalysts in the two atmospheres. On earth, they serve to convert odd oxygen (atomic oxygen and ozone) to molecular oxygen. On Venus they have a similar effect, but in addition they accelerate the reactions of atomic and molecular oxygen with carbon monoxide. The latter process occurs by a unique combination of ClOx catalysis and sulful dioxide photosensitization. The mechanism provides an explanation for the very low extent of carbon dioxide decomposition by sunlight in the Venus atmosphere.

[The effect of firing times on the chroma of tetragonal zirconia polycrystal by adding rare-earth oxides].

PubMed

Gao, Yan; Zhang, Fu-qiang; Huang, Hui; Gui, Lin-hua

2010-10-01

The aim of this study is to evaluate whether the firing times affect the chroma of zirconia by adding rare-earth oxides. Six kinds (S1, S2, S3, S4, S5, S6) of tooth-like yttria stabilized tetragonal zirconia polycrystal (Y-TZP) were available by introducing internal colorating technology, the color were gauged with ShadeEye NCC chromatometry instrument, and one-way ANOVA was used to analysis the color of each kind of tooth-like zirconia after 1, 2, 3, 4, 5 times firing individually. After 1, 2, 3, 4, 5 times firing respectively, the chromatic aberration ranged between 0.10-1.47 merely. The luminosity of three kinds (S1, S2, S6) of tooth-like zirconia were decreased (P < 0.05), the luminosity of the other three kinds (S3, S4, S5) of tooth-like zirconia were not obviously changed (P > 0.05), as for the hue and chroma, no significant differences were found (P > 0.05). There are no significant influence on the color of tooth-like Y-TZP after 1, 2, 3, 4, 5 times firing respectively, the chroma of yttria stabilized tetragonal zirconia polycrystal by adding rare-earth oxides are with high stability.

Rethinking early Earth phosphorus geochemistry

PubMed Central

Pasek, Matthew A.

2008-01-01

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO32−), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks. PMID:18195373

Rethinking early Earth phosphorus geochemistry.

PubMed

Pasek, Matthew A

2008-01-22

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO(3)(2-)), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks.

TEM and HRTEM study of oxide particles in an Al-alloyed high-Cr oxide dispersion strengthened ferritic steel with Hf addition

NASA Astrophysics Data System (ADS)

Dou, Peng; Kimura, Akihiko; Kasada, Ryuta; Okuda, Takanari; Inoue, Masaki; Ukai, Shigeharu; Ohnuki, Somei; Fujisawa, Toshiharu; Abe, Fujio; Jiang, Shan; Yang, Zhigang

2017-03-01

The nanoparticles in an Al-alloyed high-Cr oxide dispersion strengthened (ODS) ferritic steel with Hf addition, i.e., SOC-16 (Fe-15Cr-2W-0.1Ti-4Al-0.62Hf-0.35Y2O3), have been examined by transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). Relative to an Al-alloyed high-Cr ODS ferritic steel without Hf addition, i.e., SOC-9 (Fe-15.5Cr-2W-0.1Ti-4Al-0.35Y2O3), the dispersion morphology and coherency of the oxide nanoparticles in SOC-16 were significantly improved. Almost all the small nanoparticles (diameter <10 nm) in SOC-16 were found to be consistent with cubic Y2Hf2O7 oxides with the anion-deficient fluorite structure and coherent with the bcc steel matrix. The larger particles (diameter >10 nm) were also mainly identified as cubic Y2Hf2O7 oxides with the anion-deficient fluorite structure. The results presented here are compared with those of SOC-9 with a brief discussion of the underlying mechanisms of the unusual thermal and irradiation stabilities of the oxides as well as the superior strength, excellent irradiation tolerance and extraordinary corrosion resistance of SOC-16.

Effects of Rare Earth Metals on Steel Microstructures

PubMed Central

Pan, Fei; Zhang, Jian; Chen, Hao-Long; Su, Yen-Hsun; Kuo, Chia-Liang; Su, Yen-Hao; Chen, Shin-Hau; Lin, Kuan-Ju; Hsieh, Ping-Hung; Hwang, Weng-Sing

2016-01-01

Rare earth metals are used in semiconductors, solar cells and catalysts. This review focuses on the background of oxide metallurgy technologies, the chemical and physical properties of rare earth (RE) metals, the background of oxide metallurgy, the functions of RE metals in steelmaking, and the influences of RE metals on steel microstructures. Future prospects for RE metal applications in steelmaking are also presented. PMID:28773545

Oxidative Addition and Reductive Elimination at Main-Group Element Centers.

PubMed

Chu, Terry; Nikonov, Georgii I

2018-04-11

Oxidative addition and reductive elimination are key steps in a wide variety of catalytic reactions mediated by transition-metal complexes. Historically, this reactivity has been considered to be the exclusive domain of d-block elements. However, this paradigm has changed in recent years with the demonstration of transition-metal-like reactivity by main-group compounds. This Review highlights the substantial progress achieved in the past decade for the activation of robust single bonds by main-group compounds and the more recently realized activation of multiple bonds by these elements. We also discuss the significant discovery of reversible activation of single bonds and distinct examples of reductive elimination at main-group element centers. The review consists of three major parts, starting with oxidative addition of single bonds, proceeding to cleavage of multiple bonds, and culminated by the discussion of reversible bond activation and reductive elimination. Within each subsection, the discussion is arranged according to the type of bond being cleaved or formed and considers elements from the left to the right of each period and down each group of the periodic table. The majority of results discussed in this Review come from the past decade; however, earlier reports are also included to ensure completeness.

Intensification of oxidation capacity using chloroalkanes as additives in hydrodynamic and acoustic cavitation reactors.

PubMed

Chakinala, Anand G; Gogate, Parag R; Chand, Rashmi; Bremner, David H; Molina, Raúl; Burgess, Arthur E

2008-03-01

The effect of the presence and absence of the chloroalkanes, dichloromethane (CH(2)Cl(2)), chloroform (CHCl(3)) and carbon tetrachloride (CCl(4)) on the extent of oxidation of aqueous I(-) to I(3)(-) has been investigated in (a) a liquid whistle reactor (LWR) generating hydrodynamic cavitation and (b) an ultrasonic probe, which produces acoustic cavitation. The aim has been to examine the intensification achieved in the extent of oxidation due to the generation of additional free radicals/oxidants in the reactor as a result of the presence of chloroalkanes. It has been observed that the extent of increase in the oxidation reaction is strongly dependent on the applied pressure in the case of the LWR. Also, higher volumes of the chloroalkanes favour the intensification and the order of effectiveness is CCl(4)>CHCl(3)>CH(2)Cl(2). However, the results with the ultrasonic probe suggest that an optimum concentration of CH(2)Cl(2) or CHCl(3) exists beyond which there is little increase in the extent of observed intensification. For CCl(4), however, no such optimum concentration was observed and the extent of increase in the rates of oxidation reaction rose with the amount of CCl(4) added. Stage wise addition of the chloroalkanes was found to give marginally better results in the case of the ultrasonic probe as compared to bulk addition at the start of the run. Although CCl(4) is the most effective, its toxicity and carcinogenicity may mean that CH(2)Cl(2) and CHCl(3) offer a safer viable alternative and the present work should be useful in establishing the amount of chloroalkanes required for obtaining a suitable degree of intensification.

Atmospheric Production of Perchlorate on Earth and Mars

NASA Astrophysics Data System (ADS)

Claire, M.; Catling, D. C.; Zahnle, K. J.

2009-12-01

Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

One Electron-Initiated Two-Electron Oxidation of Water by Aluminum Porphyrins with Earth's Most Abundant Metal.

PubMed

Kuttassery, Fazalurahman; Mathew, Siby; Sagawa, Shogo; Remello, Sebastian Nybin; Thomas, Arun; Yamamoto, Daisuke; Onuki, Satomi; Nabetani, Yu; Tachibana, Hiroshi; Inoue, Haruo

2017-05-09

We report herein a new molecular catalyst for efficient water splitting, aluminum porphyrins (tetra-methylpyridiniumylporphyrinatealuminum: AlTMPyP), containing earth's most abundant metal as the central ion. One-electron oxidation of the aluminum porphyrin initiates the two-electron oxidation of water to form hydrogen peroxide as the primary reaction product with the lowest known overpotential (97 mV). The aluminum-peroxo complex was detected by a cold-spray ionization mass-spectrometry in high-resolution MS (HRMS) mode and the structure of the intermediate species was further confirmed using laser Raman spectroscopy, indicating the hydroperoxy complex of AlTMPyP to be the key intermediate in the reaction. The two-electron oxidation of water to form hydrogen peroxide was essentially quantitative, with a Faradaic efficiency of 99 %. The catalytic reaction was found to be highly efficient, with a turnover frequency up to ∼2×10 4  s -1 . A reaction mechanism is proposed involving oxygen-oxygen bond formation by the attack of a hydroxide ion on the oxyl-radical-like axial ligand oxygen atom in the one-electron-oxidized form of AlTMPyP(O - ) 2 , followed by a second electron transfer to the electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impacts of halogen additions on mercury oxidation, in a slipstream selective catalyst reduction (SCR), reactor when burning sub-bituminous coal.

PubMed

Cao, Yan; Gao, Zhengyang; Zhu, Jiashun; Wang, Quanhai; Huang, Yaji; Chiu, Chengchung; Parker, Bruce; Chu, Paul; Pant, Wei-Ping

2008-01-01

This paper presents a comparison of impacts of halogen species on the elemental mercury (Hg(0)) oxidation in a real coal-derived flue gas atmosphere. It is reported there is a higher percentage of Hg(0) in the flue gas when burning sub-bituminous coal (herein Powder River Basin (PRB) coal) and lignite, even with the use of selective catalytic reduction (SCR). The higher Hg(0)concentration in the flue gas makes it difficult to use the wet-FGD process for the mercury emission control in coal-fired utility boilers. Investigation of enhanced Hg(0) oxidation by addition of hydrogen halogens (HF, HCl, HBr, and HI) was conducted in a slipstream reactor with and without SCR catalysts when burning PRB coal. Two commercial SCR catalysts were evaluated. SCR catalyst no. 1 showed higher efficiencies of both NO reduction and Hg(0) oxidation than those of SCR catalyst no. 2. NH3 addition seemed to inhibit the Hg(0) oxidation, which indicated competitive processes between NH3 reduction and Hg(0) oxidation on the surface of SCR catalysts. The hydrogen halogens, in the order of impact on Hg(0) oxidation, were HBr, HI, and HCl or HF. Addition of HBr at approximately 3 ppm could achieve 80% Hg(0) oxidation. Addition of HI at approximately 5 ppm could achieve 40% Hg(0) oxidation. In comparison to the empty reactor, 40% Hg(0) oxidation could be achieved when HCl addition was up to 300 ppm. The enhanced Hg(0) oxidation by addition of HBr and HI seemed not to be correlated to the catalytic effects by both evaluated SCR catalysts. The effectiveness of conversion of hydrogen halogens to halogen molecules or interhalogens seemed to be attributed to their impacts on Hg(0) oxidation.

[Interface compatibility between tooth-like yttria-stabilized tetragonal zirconia polycrystal by adding rare-earth oxide and Vita VM9 veneering porcelain].

PubMed

Gao, Yan; Zhang, Fu-qiang; He, Fan

2011-10-01

To evaluate the interface compatibility between tooth-like yttria-stabilized tetragonal zirconia polycrystal(Y-TZP) by adding rare-earth oxide and Vita VM9 veneering porcelain. Six kinds(S1,S2,S3,S4,S5,S6) of tooth-like yttria stabilized tetragonal zirconia polycrystal were made by introducing internal colorating technology to detect the thermal shock resistance and interface bonding strength with Vita VM9 Bsaedentin. Statistical analysis was performed using SAS6.12 software package. There was no gap between the layers via hot shocking test.The shear bonding strength between Y-TZP and VitaVM9 was higher and the value was (36.03±3.82) to (37.98±4.89) MPa. By adding rare-earth oxide to yttria-stabilized tetragonal zirconia polycrystal ,better compatibility between the layer (TZP and Vita VM9) can be formed which is of better interface integrate and available for clinical applications.

Evolution of Earth-like Extrasolar Planetary Atmospheres: Assessing the Atmospheres and Biospheres of Early Earth Analog Planets with a Coupled Atmosphere Biogeochemical Model

NASA Astrophysics Data System (ADS)

Gebauer, S.; Grenfell, J. L.; Stock, J. W.; Lehmann, R.; Godolt, M.; von Paris, P.; Rauer, H.

2017-01-01

Understanding the evolution of Earth and potentially habitable Earth-like worlds is essential to fathom our origin in the Universe. The search for Earth-like planets in the habitable zone and investigation of their atmospheres with climate and photochemical models is a central focus in exoplanetary science. Taking the evolution of Earth as a reference for Earth-like planets, a central scientific goal is to understand what the interactions were between atmosphere, geology, and biology on early Earth. The Great Oxidation Event in Earth's history was certainly caused by their interplay, but the origin and controlling processes of this occurrence are not well understood, the study of which will require interdisciplinary, coupled models. In this work, we present results from our newly developed Coupled Atmosphere Biogeochemistry model in which atmospheric O2 concentrations are fixed to values inferred by geological evidence. Applying a unique tool (Pathway Analysis Program), ours is the first quantitative analysis of catalytic cycles that governed O2 in early Earth's atmosphere near the Great Oxidation Event. Complicated oxidation pathways play a key role in destroying O2, whereas in the upper atmosphere, most O2 is formed abiotically via CO2 photolysis. The O2 bistability found by Goldblatt et al. (2006) is not observed in our calculations likely due to our detailed CH4 oxidation scheme. We calculate increased CH4 with increasing O2 during the Great Oxidation Event. For a given atmospheric surface flux, different atmospheric states are possible; however, the net primary productivity of the biosphere that produces O2 is unique. Mixing, CH4 fluxes, ocean solubility, and mantle/crust properties strongly affect net primary productivity and surface O2 fluxes. Regarding exoplanets, different "states" of O2 could exist for similar biomass output. Strong geological activity could lead to false negatives for life (since our analysis suggests that reducing gases remove O2 that

Microstructure of a base metal thick film system. [Glass frit with base metal oxide addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mentley, D.E.

1976-06-01

A base metal thick film conductor system using glass frits with base metal oxide additions was investigated as metallization for hybrid microcircuits. Application of previous work on wetting and chemical bonding was made to this system. The observation of changes in the properties of the thick film was made by photomicrographs of screened samples and sheet resistivity measurements. In addition to the chemical and wetting properties, the effect of glass frit particle size on conductivity was also analyzed. The base metal oxide addition was found to produce a more consistent thick film conductor at low volume percentages of metal bymore » inhibiting the formation of low melting redox reaction products.« less

Geobiology: A Conceptual Framework for Understanding Earth's Surface

NASA Astrophysics Data System (ADS)

Sumner, D. Y.

2016-12-01

A topic of study becomes a new field when it provides a useful conceptual framework for understanding suites of important processes. Geobiology integrates microbial biology with Earth sciences in a way that allows us to ask - and answer - deeper questions about Earth and the life on it. Recent studies of the oxidation of Earth's surface exemplify the impact of Geobiology as a new field. For decades, scientists have understood that Earth's surface was oxidized by photosynthesis. Geochemical records indicate dramatic redox changes both globally, e.g. the loss of MIF sulfur signatures due to formation of an ozone layer, and locally, as preserved in sedimentary rocks. However, these records depend critically on the dynamics of both the global biosphere and local microbial ecology. For example, an increase in global redox due to photosynthetic iron oxidation has different biogeochemical implications than an increase from oxygenic photosynthesis; O2 reacts very differently with organic matter and minerals than iron oxyhydroxides do, influencing microbial ecology as well as potential geochemical signatures in sedimentary rocks. Thus, studies of modern microbial communities provide insights into the interactions among metabolisms and geochemical gradients that have shaped Earth's redox history. For example, the ability of cyanobacteria to create O2 oases in benthic mats and soils on land provides a new framework for evaluating redox-sensitive elemental fluxes to the ocean. Similarly, genomic studies of Cyanobacteria have revealed close relatives, Melainabacteria, that are mostly obligate anaerobes. The evolutionary relationships between these two groups, as preserved in their genomes, reflect important microbial processes that led to oxidation of Earth's surface. By combining insights from microbial biology and sedimentary geochemistry, geobiologists will develop significantly more accurate models of the interactions between life and Earth.

High-Temperature Oxidation of Fe3Al Intermetallic Alloy Prepared by Additive Manufacturing LENS

PubMed Central

Łyszkowski, Radosław

2015-01-01

The isothermal oxidation of Fe-28Al-5Cr (at%) intermetallic alloy microalloyed with Zr and B (<0.08 at%) in air atmosphere, in the temperature range of 1000 to 1200 °C, was studied. The investigation was carried out on the thin-walled (<1 mm) elements prepared by Laser Engineered Net Shaping (LENS) from alloy powder of a given composition. Characterization of the specimens, after the oxidation, was conducted using X-ray diffraction (XRD) and scanning electron microscopy (SEM, with back-scatter detector (BSE) and energy-dispersive X-ray spectroscopy (EDS) attachments). The investigation has shown, that the oxidized samples were covered with a thin, homogeneous α-Al2O3 oxide layers. The intensity of their growth indicates that the material lost its resistance to oxidation at 1200 °C. Structural analysis of the thin-walled components’ has not shown intensification of the oxidation process at the joints of additive layers. PMID:28788014

Synthesis of the missing oxide of xenon, XeO2, and its implications for Earth's missing xenon.

PubMed

Brock, David S; Schrobilgen, Gary J

2011-04-27

The missing Xe(IV) oxide, XeO(2), has been synthesized at 0 °C by hydrolysis of XeF(4) in water and 2.00 M H(2)SO(4(aq)). Raman spectroscopy and (16/18)O isotopic enrichment studies indicate that XeO(2) possesses an extended structure in which Xe(IV) is oxygen bridged to four neighboring oxygen atoms to give a local square-planar XeO(4) geometry based on an AX(4)E(2) valence shell electron pair repulsion (VSEPR) arrangement. The vibrational spectra of Xe(16)O(2) and Xe(18)O(2) amend prior vibrational assignments of xenon doped SiO(2) and are in accordance with prior speculation that xenon depletion from the Earth's atmosphere may occur by xenon insertion at high temperatures and high pressures into SiO(2) in the Earth's crust.

The cyclic oxidation resistance at 1200 C of beta-NiAl, FeAl, and CoAl alloys with selected third element additions

NASA Technical Reports Server (NTRS)

Barrett, C. A.; Titran, R. H.

1992-01-01

The intermetallic compounds Beta-NiAl, FeAl, and CoAl were tested in cyclic oxidation with selected third element alloy additions. Tests in static air for 200 1-hr cycles at 1200 C indicated by specific weight change/time data and x-ray diffraction analysis that the 5 at percent alloy additions did not significantly improve the oxidation resistance over the alumina forming baseline alloys without the additions. Many of the alloy additions were actually deleterious. Ta and Nb were the only alloy additions that actually altered the nature of the oxide(s) formed and still maintained the oxidation resistance of the protective alumina scale.

Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohd Fadzil, Syazwani Binti; Hrma, Pavel R.; Schweiger, Michael J.

Pyroprocessing is a reprocessing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the matrix at high loadings. Crystallization that occurs inmore » waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.« less

Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

NASA Astrophysics Data System (ADS)

Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.; Riley, Brian J.

2015-10-01

Pyroprocessing is are processing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the glass matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

Intrinsic hydrophilic nature of epitaxial thin-film of rare-earth oxide grown by pulsed laser deposition.

PubMed

Prakash, Saurav; Ghosh, Siddhartha; Patra, Abhijeet; Annamalai, Meenakshi; Motapothula, Mallikarjuna Rao; Sarkar, Soumya; Tan, Sherman J R; Zhunan, Jia; Loh, Kian Ping; Venkatesan, T

2018-02-15

Herein, we report a systematic study of water contact angle (WCA) of rare-earth oxide thin-films. These ultra-smooth and epitaxial thin-films were grown using pulsed laser deposition and then characterized using X-Ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), and atomic force microscopy (AFM). Through both the traditional sessile drop and the novel f-d method, we found that the films were intrinsically hydrophilic (WCA < 10°) just after being removed from the growth chamber, but their WCAs evolved with an exposure to the atmosphere with time to reach their eventual saturation values near 90° (but always stay 'technically' hydrophilic). X-Ray photoelectron spectroscopy analysis was used to further investigate qualitatively the nature of hydrocarbon contamination on the freshly prepared as well as the environmentally exposed REO thin-film samples as a function of the exposure time after they were removed from the deposition chamber. A clear correlation between the carbon coverage of the surface and the increase in WCA was observed for all of the rare-earth films, indicating the extrinsic nature of the surface wetting properties of these films and having no relation to the electronic configuration of the rare-earth atoms as proposed by Azimi et al.

Photoelectrochemical enhancement of ZnO/BiVO4/ZnFe2O4/rare earth oxide hetero-nanostructures

NASA Astrophysics Data System (ADS)

She, Xuefeng; Zhang, Zhuo; Baek, Minki; Yong, Kijung

2018-01-01

Over the decades, researchers have made great efforts to turn the world into a cleaner place through efficient recycling of industrial waste and developing of green energy. Here we demonstrate a prototype heterostructure photoelectrochemical (PEC) cell fabricated using recycled industrial waste. ZnFe2O4 (ZFO) nanorod (NR) clusters were synthesized on the BiVO4@ZnO hetero-nanostructures using recycled rare earth oxide (REO) slags as Fe source. The NR-based PEC cell exhibited a significantly enhanced photon to hydrogen conversion efficiency over the entire UV and visible spectrum. Further study demonstrates that the photo-carrier separation and migration processes can be facilitated by the cascade band alignment of the heterostructure and the clustered nanostructure network. In addition, the life-time of the photo-carriers can be enhanced by the REO passivation layer, leading to a further increased PEC performance. Our results present a novel approach for high efficiency PEC cells, and offer great promises to the efficient recycling of industrial waste for clean renewable energy applications.

Graphene Oxide: An All-in-One Processing Additive for 3D Printing.

PubMed

García-Tuñón, Esther; Feilden, Ezra; Zheng, Han; D'Elia, Eleonora; Leong, Alan; Saiz, Eduardo

2017-09-27

Many 3D printing technologies are based on the development of inks and pastes to build objects through droplet or filament deposition (the latter also known as continuous extrusion, robocasting, or direct ink writing). Controlling and tuning rheological behavior is key for successful manufacturing using these techniques. Different formulations have been proposed, but the search continues for approaches that are clean, flexible, robust and that can be adapted to a wide range of materials. Here, we show how graphene oxide (GO) enables the formulation of water-based pastes to print a wide variety of materials (polymers, ceramics, and steel) using robocasting. This work combines flow and oscillatory rheology to provide further insights into the rheological behavior of suspensions combining GO with other materials. Graphene oxide can be used to manipulate the viscoelastic response, enabling the formulation of pastes with excellent printing behavior that combine shear thinning flow and a fast recovery of their elastic properties. These inks do not contain other additives, only GO and the material of interest. As a proof of concept, we demonstrate the 3D printing of additive-free graphene oxide structures as well as polymers, ceramics, and steel. Due to its amphiphilic nature and 2D structure, graphene oxide plays multiple roles, behaving as a dispersant, viscosifier, and binder. It stabilizes suspensions of different powders, modifies the flow and viscoelasticity of materials with different chemistries, particle sizes and shapes, and binds the particles together, providing green strength for manual handling. This approach enables printing complex 3D ceramic structures using robocasting with similar properties to alternative formulations, thus demonstrating the potential of using 2D colloids in materials manufacturing.

The oxidation state of the mantle and the extraction of carbon from Earth's interior.

PubMed

Stagno, Vincenzo; Ojwang, Dickson O; McCammon, Catherine A; Frost, Daniel J

2013-01-03

Determining the oxygen fugacity of Earth's silicate mantle is of prime importance because it affects the speciation and mobility of volatile elements in the interior and has controlled the character of degassing species from the Earth since the planet's formation. Oxygen fugacities recorded by garnet-bearing peridotite xenoliths from Archaean lithosphere are of particular interest, because they provide constraints on the nature of volatile-bearing metasomatic fluids and melts active in the oldest mantle samples, including those in which diamonds are found. Here we report the results of experiments to test garnet oxythermobarometry equilibria under high-pressure conditions relevant to the deepest mantle xenoliths. We present a formulation for the most successful equilibrium and use it to determine an accurate picture of the oxygen fugacity through cratonic lithosphere. The oxygen fugacity of the deepest rocks is found to be at least one order of magnitude more oxidized than previously estimated. At depths where diamonds can form, the oxygen fugacity is not compatible with the stability of either carbonate- or methane-rich liquid but is instead compatible with a metasomatic liquid poor in carbonate and dominated by either water or silicate melt. The equilibrium also indicates that the relative oxygen fugacity of garnet-bearing rocks will increase with decreasing depth during adiabatic decompression. This implies that carbon in the asthenospheric mantle will be hosted as graphite or diamond but will be oxidized to produce carbonate melt through the reduction of Fe(3+) in silicate minerals during upwelling. The depth of carbonate melt formation will depend on the ratio of Fe(3+) to total iron in the bulk rock. This 'redox melting' relationship has important implications for the onset of geophysically detectable incipient melting and for the extraction of carbon dioxide from the mantle through decompressive melting.

Production method for making rare earth compounds

DOEpatents

McCallum, R.W.; Ellis, T.W.; Dennis, K.W.; Hofer, R.J.; Branagan, D.J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g., a transition metal and optional boron), and a carbide-forming element (e.g., a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g., Nd{sub 2}Fe{sub 14}B or LaNi{sub 5}) and a carbide of the carbide-forming element are formed.

Production method for making rare earth compounds

DOEpatents

McCallum, R. William; Ellis, Timothy W.; Dennis, Kevin W.; Hofer, Robert J.; Branagan, Daniel J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g. a transition metal and optional boron), and a carbide-forming element (e.g. a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g. Nd.sub.2 Fe.sub.14 B or LaNi.sub.5) and a carbide of the carbide-forming element are formed.

Carbon cycling and snowball Earth.

PubMed

Goddéris, Yves; Donnadieu, Yannick

2008-12-18

The possibility that Earth witnessed episodes of global glaciation during the latest Precambrian challenges our understanding of the physical processes controlling the Earth's climate. Peltier et al. suggest that a 'hard snowball Earth' state may have been prevented owing to the release of CO(2) from the oxidation of dissolved organic carbon (DOC) in the ocean as the temperature decreased. Here we show that the model of Peltier et al. is not self-consistent as it implies large fluctuations of the ocean alkalinity content without providing any processes to account for it. Our findings suggest that the hard snowball Earth hypothesis is still valid.

Nitrogen Oxides in Early Earth's Atmosphere as Electron Acceptors for Life's Emergence

NASA Astrophysics Data System (ADS)

Wong, Michael L.; Charnay, Benjamin D.; Gao, Peter; Yung, Yuk L.; Russell, Michael J.

2017-10-01

We quantify the amount of nitrogen oxides (NOx) produced through lightning and photochemical processes in the Hadean atmosphere to be available in the Hadean ocean for the emergence of life. Atmospherically generated nitrate (NO3-) and nitrite (NO2-) are the most attractive high-potential electron acceptors for pulling and enabling crucial redox reactions of autotrophic metabolic pathways at submarine alkaline hydrothermal vents. The Hadean atmosphere, dominated by CO2 and N2, will produce nitric oxide (NO) when shocked by lightning. Photochemical reactions involving NO and H2O vapor will then produce acids such as HNO, HNO2, HNO3, and HO2NO2 that rain into the ocean. There, they dissociate into or react to form nitrate and nitrite. We present new calculations based on a novel combination of early-Earth global climate model and photochemical modeling, and we predict the flux of NOx to the Hadean ocean. In our 0.1-, 1-, and 10-bar pCO2 models, we calculate the NOx delivery to be 2.4 × 105, 6.5 × 108, and 1.9 × 108 molecules cm-2 s-1. After only tens of thousands to tens of millions of years, these NOx fluxes are expected to produce sufficient (micromolar) ocean concentrations of high-potential electron acceptors for the emergence of life.

Metal oxide films on metal

DOEpatents

Wu, Xin D.; Tiwari, Prabhat

1995-01-01

A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

Fabrication and secondary-phase crystallization of rare-earth disilicate-silicon nitride ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinibulk, M.K.; Thomas, G.; Johnson, S.M.

1992-08-01

In this paper, the fabrication and intergranular-phase devitrification of silicon nitride densified with rare-earth (RE) oxide additives is investigated. The additions of the oxides of Sm, Gd, Dy, Er, and Yb, having high melting points and behaving similarly to Y[sub 2]O[sub 3], were compositionally controlled to tailor a microstructure with a crystalline secondary phase of RE[sub 2]Si[sub 2]O[sub 7]. The lanthanide oxides were found to be ass effective as Y[sub 2]O[sub 3] in densifying Si[sub 3]N[sub 4], resulting in identical microstructures and densities of 98-99% of theoretical density. The crystallization behavior of all six disilicates was similar, characterized by amore » limited nucleation and rapid growth mechanism resulting in large single crystals. Complete crystallization of the intergranular phase was obtained with the exception of a thin residual amorphous film which was observed at interfaces and believed to be rich in impurities, the cause of incomplete devitrification.« less

Proterozoic low-Ti iron-oxide deposits in New York and New Jersey: relation to Fe-oxide (Cu-U-Au-rare earth element) deposits and tectonic implications

USGS Publications Warehouse

Foose, M.P.; McLelland, J.M.

1995-01-01

Low-Ti iron-oxide deposits in exposed Grenville-age rocks of New York and New Jersey belong to a distinct class of iron-oxide (Cu-U-Au-rare earth element [REE]) deposits that includes similar iron deposits in southeastern Missouri and the Kiruna district of Sweden, the giant Olympic Dam U-Cu-Au-Ag deposit (Australia), and the Bayan Obo REE-Nb deposit (China). Most of the New York-New Jersey deposits exhibit features consistent with a hydrothermal origin and define a regionally significant metallogenic event that provides important clues to the evolution of this part of the Grenville orogen. In the Adirondacks, the tectonic setting of these deposits is consistent with postorogenic uplift and extensive crustal melting at 1070-1050 Ma that was accompanied by late tectonic to posttectonic deposition of iron. -Authors

A reactive distillation process for the treatment of LiCl-KCl eutectic waste salt containing rare earth chlorides

NASA Astrophysics Data System (ADS)

Eun, H. C.; Choi, J. H.; Kim, N. Y.; Lee, T. K.; Han, S. Y.; Lee, K. R.; Park, H. S.; Ahn, D. H.

2016-11-01

The pyrochemical process, which recovers useful resources (U/TRU metals) from used nuclear fuel using an electrochemical method, generates LiCl-KCl eutectic waste salt containing radioactive rare earth chlorides (RECl3). It is necessary to develop a simple process for the treatment of LiCl-KCl eutectic waste salt in a hot-cell facility. For this reason, a reactive distillation process using a chemical agent was achieved as a method to separate rare earths from the LiCl-KCl waste salt. Before conducting the reactive distillation, thermodynamic equilibrium behaviors of the reactions between rare earth (Nd, La, Ce, Pr) chlorides and the chemical agent (K2CO3) were predicted using software. The addition of the chemical agent was determined to separate the rare earth chlorides into an oxide form using these equilibrium results. In the reactive distillation test, the rare earth chlorides in LiCl-KCl eutectic salt were decontaminated at a decontamination factor (DF) of more than 5000, and were mainly converted into oxide (Nd2O3, CeO2, La2O3, Pr2O3) or oxychloride (LaOCl, PrOCl) forms. The LiCl-KCl was purified into a form with a very low concentration (<1 ppm) for the rare earth chlorides.

Oxide inclusions in laser additive manufactured stainless steel and their effects on impact toughness and stress corrosion cracking behavior

NASA Astrophysics Data System (ADS)

Lou, Xiaoyuan; Andresen, Peter L.; Rebak, Raul B.

2018-02-01

Intergranular and intragranular Si and Mn rich oxide inclusions are present in laser additive manufactured austenitic stainless steel. The uniform oxide dispersions in additive manufactured material promoted early initiation of microvoids and reduced its impact toughness relative to powder metallurgy (hot isostatic pressing) and wrought materials. For stress corrosion cracking in high temperature water, the silica inclusions along the grain boundaries preferentially dissolved and appeared to accelerate oxidation and caused extensive crack branching.

Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO2 Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene.

PubMed

Friedman, Beth; Brophy, Patrick; Brune, William H; Farmer, Delphine K

2016-02-02

In order to probe how anthropogenic pollutants can impact the atmospheric oxidation of biogenic emissions, we investigated how sulfur dioxide (SO2) perturbations impact the oxidation of two monoterpenes, α-and β-pinene. We used chemical ionization mass spectrometry to examine changes in both individual molecules and gas-phase bulk properties of oxidation products as a function of SO2 addition. SO2 perturbations impacted the oxidation systems of α-and β-pinene, leading to an ensemble of products with a lesser degree of oxygenation than unperturbed systems. These changes may be due to shifts in the OH:HO2 ratio from SO2 oxidation and/or to SO3 reacting directly with organic molecules. Van Krevelen diagrams suggest a shift from gas-phase functionalization by alcohol/peroxide groups to functionalization by carboxylic acid or carbonyl groups, consistent with a decreased OH:HO2 ratio. Increasing relative humidity dampens the impact of the perturbation. This decrease in oxygenation may impact secondary organic aerosol formation in regions dominated by biogenic emissions with nearby SO2 sources. We observed sulfur-containing organic compounds following SO2 perturbations of monoterpene oxidation; whether these are the result of photochemistry or an instrumental artifact from ion-molecule clustering remains uncertain. However, our results demonstrate that the two monoterpene isomers produce unique suites of oxidation products.

Effects of silicon additions on oxidation and mechanical behavior of the nickel-base superalloy B-1900

NASA Technical Reports Server (NTRS)

Miner, R. V., Jr.; Lowell, C. E.

1975-01-01

Test specimens with nominal additions of Si were tested in oxidation, thermal fatigue, sulfidation, tension, and stress rupture, and were also extensively studied metallographically. Alloy B-1900 modified with 0.6- or 1.2-wt% Si exhibited oxidation resistance equivalent to that of aluminide-coated B-1900 during cyclic, high-gas-velocity oxidation tests. Resistances to thermal fatigue and sulfidation were improved by the Si additions, but were not superior to aluminide-coated B-1900. Stress-rupture tests at 1000 C of specimens given the standard heat treatment to simulate an aluminide coating cycle showed Si to be detrimental. However, application of another heat treatment increased the rupture life of the alloy with 0.6-wt% Si to that of the unmodified B-1900 given the standard heat treatment.

Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Ward, Matthew; Pelletier, Mia

2018-05-01

The geochemical behavior of rare earth elements (REE) was investigated using weathering cells. The influence of sorption and precipitation on dissolved REE mobility and fractionation is evaluated using synthetic iron-oxides, carbonates, and phosphates. Sorption cell tests are conducted on the main lithologies of the expected waste rocks from the Montviel deposit. The sorbed materials are characterized using a scanning electron microscope (SEM) equipped with a microanalysis system (energy dispersive spectroscopy EDS) (SEM-EDS), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) in order to understand the effect of the synthetic minerals on REE mobility. The results confirm that sorption and precipitation control the mobility and fractionation of REE. The main sorbent phases are the carbonates, phosphates (present as accessory minerals in the Montviel waste rocks), and iron oxides (main secondary minerals generated upon weathering of the Montviel lithologies). The XANES results show that REE are present as trivalent species after weathering. Thermodynamic equilibrium calculations results using Visual Minteq suggest that REE could precipitate as secondary phosphates (REEPO 4 ). Copyright © 2018 Elsevier Ltd. All rights reserved.

Evaluation of AA5052 alloy anode in alkaline electrolyte with organic rare-earth complex additives for aluminium-air batteries

NASA Astrophysics Data System (ADS)

Wang, Dapeng; Li, Heshun; Liu, Jie; Zhang, Daquan; Gao, Lixin; Tong, Lin

2015-10-01

Behaviours of the AA5052 aluminium alloy anode of the alkaline aluminium-air battery are studied by the hydrogen evolution test, the electrochemical measurements and the surface analysis method. The combination of amino-acid and rare earth as electrolyte additives effectively retards the self-corrosion of AA5052 aluminium alloy in 4 M NaOH solution. It shows that the combination of L-cysteine and cerium nitrate has a synergistic effect owing to the formation of a complex film on AA5052 alloy surface. The organic rare-earth complex can decrease the anodic polarisation, suppress the hydrogen evolution and increase the anodic utilization rate.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Au/MxOy/TiO2 catalysts for CO oxidation: promotional effect of main-group, transition, and rare-earth metal oxide additives.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Zhen; Overbury, Steven; Dai, Sheng

Au/TiO2 catalysts are active for CO oxidation, but they suffer from high-temperature sintering of the gold particles, and few attempts have been made to promote or stabilize Au/TiO2. Our recent communication addressed these issues by loading gold onto Al2O3/TiO2 prepared via surface-sol-gel processing of Al(sec-OC4H9)3 on TiO2. In our current full paper, Au/Al2O3/TiO2 catalysts were prepared alternatively by thermal decomposition of Al(NO3)3 on TiO2 followed by loading gold, and the influences of the decomposition temperature and Al2O3 content were systematically surveyed. This facile method was subsequently extended to the preparation of a battery of metal oxide-modified Au/TiO2 catalysts virtually notmore » reported. It was found that Au/TiO2 modified by CaO, NiO, ZnO, Ga2O3, Y2O3, ZrO2, La2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Dy2O3, Ho2O3, Er2O3, or Yb2O3 could retain significant activity at ambient temperature even after aging in O2-He at 500 C, whereas unmodified Au/TiO2 lost its activity. Moreover, some 200 C-calcined promoted catalysts showed high activity even at about -100 C. The deactivation and regeneration of some of these new catalysts were studied. This work furnished novel catalysts for further fundamental and applied research.« less

Role of metal oxides in chemical evolution

NASA Astrophysics Data System (ADS)

Kamaluddin

2013-06-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Formation of small molecules like amino acids, organic bases, sugar etc. could have occurred in the reducing atmosphere of the primitive Earth. Polymerization of these small molecules could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

How did life survive Earth's great oxygenation?

PubMed

Fischer, Woodward W; Hemp, James; Valentine, Joan Selverstone

2016-04-01

Life on Earth originated and evolved in anoxic environments. Around 2.4 billion-years-ago, ancestors of Cyanobacteria invented oxygenic photosynthesis, producing substantial amounts of O2 as a byproduct of phototrophic water oxidation. The sudden appearance of O2 would have led to significant oxidative stress due to incompatibilities with core cellular biochemical processes. Here we examine this problem through the lens of Cyanobacteria-the first taxa to observe significant fluxes of intracellular dioxygen. These early oxygenic organisms likely adapted to the oxidative stress by co-opting preexisting systems (exaptation) with fortuitous antioxidant properties. Over time more advanced antioxidant systems evolved, allowing Cyanobacteria to adapt to an aerobic lifestyle and become the most important environmental engineers in Earth history. Copyright © 2016 Elsevier Ltd. All rights reserved.

High inflammogenic potential of rare earth oxide nanoparticles: the New Hazardous Entity.

PubMed

Han, Youngju; Lee, Dong-Keon; Kim, Sung-Hyun; Lee, Seonghan; Jeon, Soyeon; Cho, Wan-Seob

2018-05-30

Due to the exponential increase in the development and utilization of rare earth oxide nanoparticles (REO NPs) in various fields, the possibility of exposure in humans by inhalation has increased. However, there are little information about hazards of REO NPs and its mechanisms of toxicity. In this study, we evaluated the acute pulmonary inflammation using 10 REO NPs (Dy 2 O 3 , Er 2 O 3 , Eu 2 O 3 , Gd 2 O 3 La 2 O 3 , Nd 2 O 3 , Pr 6 O 11 , Sm 2 O 3 , Tb 4 O 7 , and Y 2 O 3 ) and four well-known toxic particles (CuO, NiO, ZnO, and DQ12). Minimum three doses per NP were instilled into the lungs of female Wistar rats at surface area dose metric and lung inflammation was evaluated at 24 h post-instillation by bronchoalveolar lavage fluid (BALF) analysis and histopathological observation. All types of REO NPs showed common pathological changes including mild to moderate infiltration of neutrophils and activated macrophages in the alveoli, peribronchial, and perivascular region. The inflammogenic potential evaluated by the number of granulocytes divided by the treated surface area dose showed all types of REO NPs has much higher inflammogenic potential than DQ12, ZnO, and NiO NPs. The correlation plot between the number of granulocytes and the potential for reactive oxygen species (ROS) generation showed a good correlation with exception of Pr 6 O 11 . The higher inflammogenic potential of REO NPs than that of well-known highly toxic particles imply that REO NPs need special attention for inhalation exposure and more studies are needed. In addition, the potential of ROS generation is one of the key factors producing lung inflammation by REO NPs.

The effect of hydrophilicity of graphene oxide as additive towards performance of polysulfone membrane

NASA Astrophysics Data System (ADS)

Jamalludin, Mohd Riduan; Harun, Zawati; Zakaria, M. S.; Rahim, Wan Mohd Faizal Wan Abd; Khor, C. Y.; Rosli, M. U.; Ishak, Muhammad Ikman; Nawi, M. A. M.; Shahrin, Suhaimi

2017-09-01

This study investigates the effect of hydrophilicity of graphene oxide as additive towards properties and performance on polysulfone (PSf) membrane. A polysulfone (PSf) membrane containing graphene oxide (GO) with different content was prepared via phase inversion technique. Characterization on the fabricated membrane were water contact angle measurement, porosity and mean pore size. The effects of PSf/GO were further investigated in terms of permeation test, rejection test and antifouling test. Based on the result obtained, PSf membrane incorporating with GO additive shows better capability to permeate more water compared to unfilled PSf membrane. The PSf/GO membrane were able to increase the permeate rate rapidly with the highest value is given by sample 4 (consist of 0.7 g of GO) at 571.78 J/m2h. Furthermore, water contact angle confirmed the hydrophilicity of this membrane at 62°. The transmembrane fouling activity showed that GO embedded in PSf membrane has improved tremendously. In addition, this study revealed that 0.7g of GO had the highest permeation test, rejection test and antifouling test.

Effects of plasma electrolytic oxidation process on the mechanical properties of additively manufactured porous biomaterials.

PubMed

Gorgin Karaji, Zahra; Hedayati, Reza; Pouran, Behdad; Apachitei, Iulian; Zadpoor, Amir A

2017-07-01

Metallic porous biomaterials are recently attracting more attention thanks to the additive manufacturing techniques which help produce more complex structures as compared to conventional techniques. On the other hand, bio-functional surfaces on metallic biomaterials such as titanium and its alloys are necessary to enhance the biological interactions with the host tissue. This study discusses the effect of plasma electrolytic oxidation (PEO), as a surface modification technique to produce bio-functional layers, on the mechanical properties of additively manufactured Ti6Al4V scaffolds based on the cubic unit cell. For this purpose, the PEO process with two different oxidation times was applied on scaffolds with four different values of relative density. The effects of the PEO process were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), optical microscopy as well as static and dynamic (fatigue) mechanical testing under compression. SEM results indicated pore formation on the surface of the scaffolds after oxidation with a thickness of 4.85±0.36μm of the oxide layer after 2min and 9.04±2.27μm after 5min oxidation (based on optical images). The static test results showed the high effect of relative density of porous structure on its mechanical properties. However, oxidation did not influence most of the mechanical properties such as maximum stress, yield stress, plateau stress, and energy absorption, although its effect on the elastic modulus was considerable. Under fatigue loading, none of the scaffolds failed even after 10 6 loading cycles at 70% of their yield stress. Copyright © 2017 Elsevier B.V. All rights reserved.

Tandem nucleophilic addition-Oppenauer oxidation of aromatic aldehydes to aryl ketones with triorganoaluminium reagents.

PubMed

Fu, Ying; Yang, Yanshou; Hügel, Helmut M; Du, Zhengyin; Wang, Kehu; Huang, Danfeng; Hu, Yulai

2013-07-21

In the presence of pinacolone, the in situ prepared triorganoaluminium reagents reacted with aromatic aldehydes to give ketones in moderate to high yield. We propose that the products are formed via a tandem organoaluminium reagents addition-Oppenauer oxidation sequence.

Effect of LEO Exposure on Aromatic Polymers Containing Phenylphosphine Oxide Groups

NASA Technical Reports Server (NTRS)

Lillehei, P. T.; Smith, J. G., Jr.; Connell, J. W.

2008-01-01

As part of the Materials on The International Space Station Experiment (MISSE), aromatic polymers containing phenylphosphine oxide groups were exposed to low Earth orbit for approx.4 years. All of the aromatic polymers containing phenylphosphine oxide groups survived the exposure despite the high fluence of atomic oxygen that completely eroded other polymer films such as Kapton(TradeMark) and Mylar(Trademark) of comparable or greater thickness. The samples were characterized for changes in physical properties, thermal/optical properties surface chemistry, and surface topography. The data from the polymer samples on MISSE were compared to samples from the same batch of material stored under ambient conditions on Earth. In addition, comparisons were made between the MISSE samples and those subjected to shorter term space flight exposures. The results of these analyses will be presented.

Organic Aerosols in the Presence of CO2 in the Early Earth and Exoplanets: UV-Vis Refractive Indices of Oxidized Tholins

NASA Astrophysics Data System (ADS)

Gavilan, Lisseth; Broch, Laurent; Carrasco, Nathalie; Fleury, Benjamin; Vettier, Ludovic

2017-10-01

In this experimental study we investigate the role of atmospheric CO2 on the optical properties of organic photochemical aerosols. To this end, we add CO2 to a N2:CH4 gas mixture used in a plasma typically used for Titan studies. We produce organic thin films (tholins) in plasmas where the CO2/CH4 ratio is increased from 0 to 4. We measure these films via spectrometric ellipsometry and apply a Tauc-Lorentz model, used for optically transparent materials, to obtain the thickness of the thin film, its optical band gap, and the refractive indices in the UV-visible (270-600 nm). All samples present a significant absorption band in the UV. According to the Tauc-Lorentz model, as the CO2/CH4 ratio is quadrupled, the position of the UV band is shifted from ˜177 nm to 264 nm while its strength is quadrupled. Consequently, we infer that oxidized organic aerosols absorb more efficiently at longer UV wavelengths than reduced aerosols. Our laboratory wavelength-tabulated UV-vis refractive indices provide new constraints to atmospheric models of the early Earth and Earth-like exoplanets including photochemical hazes formed under increasingly oxidizing conditions.

Time-resolved XAFS spectroscopic studies of B-H and N-H oxidative addition to transition metal catalysts relevant to hydrogen storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bitterwolf, Thomas E.

2014-12-09

Successful catalytic dehydrogenation of aminoborane, H 3NBH 3, prompted questions as to the potential role of N-H oxidative addition in the mechanisms of these processes. N-H oxidative addition reactions are rare, and in all cases appear to involve initial dative bonding to the metal by the amine lone pairs followed by transfer of a proton to the basic metal. Aminoborane and its trimethylborane derivative block this mechanism and, in principle, should permit authentic N-H oxidative attrition to occur. Extensive experimental work failed to confirm this hypothesis. In all cases either B-H complexation or oxidative addition of solvent C-H bonds dominatemore » the chemistry.« less

Mineral resource of the month: rare earths

USGS Publications Warehouse

Hedrick, James B.

2004-01-01

As if classified as a top-secret project, the rare earths have been shrouded in secrecy. The principal ore mineral of the group, bastnäsite, rarely appears in the leading mineralogy texts. The long names of the rare-earth elements and some unusual arrangements of letters, many Scandinavian in origin, may have intimidated even those skilled in phonics. Somewhat obscurely labeled, the rare earths are neither rare nor earths (the historical term for oxides). They are a relatively abundant group of metallic elements that occur in nature as nonmetallic compounds and have hundreds of commercial applications.

Tribological properties of graphene oxide and carbon spheres as lubricating additives

NASA Astrophysics Data System (ADS)

Song, Haojie; Wang, Zhiqiang; Yang, Jin

2016-10-01

The purpose of this paper was to investigate the tribological properties of carbon materials with various morphologies [i.e., graphene oxide (GO) and carbon spheres (CSs)] utilized as lubricating additives on a ball-plate tribotester. The morphology and spectroscopy characterization of GO and CSs were investigated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry, and thermogravimetric analysis. Friction and wear properties of the sunflower seed oil filled with GO and CSs were investigated by using a MS-T3000 ball-on-disk apparatus. Results show that the sunflower seed oil containing 0.3 wt% GO nanosheets exhibited a substantial diminution in friction and wear compared with the 3.0 wt% CSs as sunflower seed oil additives. Formation of low-shear strength tribofilms containing GO and its self-lubricating behavior was the key factor in reduction of the friction and prevention from wear and deformation. In addition, friction mechanism of CSs was also discussed.

Radioactive rare-earth deposit at Scrub Oaks mine, Morris County, New Jersey

USGS Publications Warehouse

Klemic, Harry; Heyl, A.V.; Taylor, Audrey R.; Stone, Jerome

1959-01-01

A deposit of rare-earth minerals in the Scrub Oaks iron mine, Morris County, N. J., was mapped and sampled in 1955. The rare-earth minerals are mainly in coarse-grained magnetite ore and in pegmatite adjacent to it. Discrete bodies of rare-earth-bearing magnetite ore apparently follow the plunge of the main magnetite ore body at the north end of the mine. Radioactivity of the ore containing rare earths is about 0.2 to 0.6 mllliroentgens per hour. The principal minerals of the deposit are quartz, magnetite, hematite, albiteoligoclase, perthite and antiperthite. Xenotime and doverite aggregates and bastnaesite with intermixed leucoxene are the most abundant rare-earth minerals, and zircon, sphene, chevkinite, apatite, and monazite are of minor abundance in the ore. The rare-earth elements are partly differentiated into cerium-rich bastnaesite, chevkinite, and monazite, and yttrium-rich xenotime and doverite. Apatite, zircon, and sphene contain both cerium and yttrium group earths. Eleven samples of radioactive ore and rock average 0.009 percent uranium, 0.062 percent thorium, 1.51 percent combined rare-earth oxides including yttrium oxide and 24.8 percent iron. Scatter diagrams of sample data show a direct correlation between equivalent uranium, uranium, thorium, and combined rare^ earth oxides. Both cerium- and yttrium-group earths are abundant in the rare-earth minerals. Radioactive magnetite ore containing rare-earth minerals probably formed as a variant of the magnetite mineralization that produced the main iron ore of the Scrub Oaks deposit. The rare-earth minerals and the iron ore were deposited contemporaneously. Zircon crystals, probably deposited at the same time, have been determined by the Larsen method to be about 550 to 600 million years old (late Precambrian age). Uranium, thorium, and rare-earth elements are potential byproducts of iron in the coarse-grained magnetite ore.

The Janus face of iron on anoxic worlds: iron oxides are both protective and destructive to life on the early Earth and present-day Mars.

PubMed

Wadsworth, Jennifer; Cockell, Charles S

2017-05-01

The surface of the early Earth was probably subjected to a higher flux of ultraviolet (UV) radiation than today. UV radiation is known to severely damage DNA and other key molecules of life. Using a liquid culture and a rock analogue system, we investigated the interplay of protective and deleterious effects of iron oxides under UV radiation on the viability of the model organism, Bacillus subtilis. In the presence of hydrogen peroxide, there exists a fine balance between iron oxide's protective effects against this radiation and its deleterious effects caused by Photo-Fenton reactions. The maximum damage was caused by a concentration of hematite of ∼1 mg/mL. Concentrations above this confer increasing protection by physical blockage of the UV radiation, concentrations below this cause less effective UV radiation blockage, but also a correspondingly less effective Photo-Fenton reaction, providing an overall advantage. These results show that on anoxic worlds, surface habitability under a high UV flux leaves life precariously poised between the beneficial and deleterious effects of iron oxides. These results have relevance to the Archean Earth, but also the habitability of the Martian surface, where high levels of UV radiation in combination with iron oxides and hydrogen peroxide can be found. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Anomalous positive flatband voltage shifts in metal gate stacks containing rare-earth oxide capping layers

NASA Astrophysics Data System (ADS)

Caraveo-Frescas, J. A.; Hedhili, M. N.; Wang, H.; Schwingenschlögl, U.; Alshareef, H. N.

2012-03-01

It is shown that the well-known negative flatband voltage (VFB) shift, induced by rare-earth oxide capping in metal gate stacks, can be completely reversed in the absence of the silicon overlayer. Using TaN metal gates and Gd2O3-doped dielectric, we measure a ˜350 mV negative shift with the Si overlayer present and a ˜110 mV positive shift with the Si overlayer removed. This effect is correlated to a positive change in the average electrostatic potential at the TaN/dielectric interface which originates from an interfacial dipole. The dipole is created by the replacement of interfacial oxygen atoms in the HfO2 lattice with nitrogen atoms from TaN.

Experimental Evaluation of Oxide Nanoparticles as Friction and Wear Improvement Additives in Motor Oil

DOE PAGES

Demas, Nicholaos G.; Erck, Robert A.; Lorenzo-Martin, Cinta; ...

2017-01-30

The effect of two nanoparticle oxides on friction and wear was studied under laboratory test conditions using a reciprocating test machine and two test configurations. The addition of these nanoparticles in base stock oil under certain conditions reduced the coefficient of friction and improved wear, but that depended on the test configuration. Examination of the rubbed surfaces showed the pronounced formation of a tribofilm in some cases, while polishing on the surface was also observed in other cases. Contact configuration is important when oxide nanoparticles are being evaluated and the conclusions about their efficacy can be vastly different.

Change of brown coal oxidation kinetic characteristics by promoting additives appending in the form of copper salts

NASA Astrophysics Data System (ADS)

Larionov, K. B.; Mishakov, I. V.; Gromov, A. A.; Zenkov, A. V.

2017-11-01

Process of brown coal oxidation with 5%wt content of copper-salt additives of various nature (Cu (NO3)2, CuSO4 and Cu(CH3COO)2) was studied. The experiment has been performed by thermogravimetric analysis at a heating rate of 2.5°C/min to a maximum temperature of 600°C in the air. Analytical evaluation of oxidation process kinetic characteristics has been conducted based on the results of TGA. It has been established that addition of initiating agents leads to significant reduction in the initial ignition temperature of coal (ΔTi = 15÷40°C), shortening of the sample warm-up time to the ignition point (Δte = 6÷12 min) and reduction of the sample burning time (Δtf = 40÷54 min). The following series of additives activity affecting ignition temperature of coals has been established: Cu(CH3COO)2 > Cu(NO3)2 > CuSO4. Additionally, the opposite can be said about the effect of additives on residence time of the sample in its combustion area (CuSO4 > Cu(NO3)2 > Cu(CH3COO)2). According to mass spectrometric analysis, presence of NOx, SO2, CO2 (intense peaks at 190÷290°C) was recorded in oxidation products of modified samples, which is explained by partial or complete decomposition of salts.

Nanocrystalline semiconductor doped rare earth oxide for the photocatalytic degradation studies on Acid Blue 113: A di-azo compound under UV slurry photoreactor.

PubMed

Suganya Josephine, G A; Mary Nisha, U; Meenakshi, G; Sivasamy, A

2015-11-01

Preventive measures for the control of environmental pollution and its remediation has received much interest in recent years due to the world-wide increase in the contamination of water bodies. Contributions of these harmful effluents are caused by the leather processing, pharmaceutical, cosmetic, textile, agricultural and other chemical industries. Nowadays, advanced oxidation processes considered to be better option for the complete destruction of organic contaminants in water and wastewater. Acid Blue 113 is a most widely used di-azo compound in leather, textile, dying and food industry as a color rending compound. In the present study, we have reported the photo catalytic degradation of Acid Blue 113 using a nanocrystalline semiconductor doped rare earth oxide as a photo catalyst under UV light irradiation. The photocatalyst was prepared by a simple precipitation technique and were characterized by XRD, FT-IR, UV-DRS and FE-SEM analysis. The experimental results proved that the prepared photo catalyst was nanocrystalline and highly active in the UV region. The UV-DRS results showed the band gap energy was 3.15eV for the prepared photo catalyst. The photodegradation efficiency was analyzed by various experimental parameters such as pH, catalyst dosage, variation of substrate concentration and effect of electrolyte addition. The photo degradation process followed a pseudo first order kinetics and was continuously monitored by UV-visible spectrophotometer. The experimental results proved the efficacy of the nanocrystalline zinc oxide doped dysprosium oxide which are highly active under UV light irradiations. It is also suggested that the prepared material would find wider applications in environmental remediation technologies to remove the carcinogenic and toxic moieties present in the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

Depositing laser-generated nanoparticles on powders for additive manufacturing of oxide dispersed strengthened alloy parts via laser metal deposition

NASA Astrophysics Data System (ADS)

Streubel, René; Wilms, Markus B.; Doñate-Buendía, Carlos; Weisheit, Andreas; Barcikowski, Stephan; Henrich Schleifenbaum, Johannes; Gökce, Bilal

2018-04-01

We present a novel route for the adsorption of pulsed laser-dispersed nanoparticles onto metal powders in aqueous solution without using any binders or surfactants. By electrostatic interaction, we deposit Y2O3 nanoparticles onto iron-chromium based powders and obtain a high dispersion of nano-sized particles on the metallic powders. Within the additively manufactured component, we show that the particle spacing of the oxide inclusion can be adjusted by the initial mass fraction of the adsorbed Y2O3 particles on the micropowder. Thus, our procedure constitutes a robust route for additive manufacturing of oxide dispersion-strengthened alloys via oxide nanoparticles supported on steel micropowders.

Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides

PubMed Central

Kim, J. Dongun; Yee, Nathan; Nanda, Vikas; Falkowski, Paul G.

2013-01-01

Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth’s history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth. PMID:23733945

Thermoelectric Properties of Barium Plumbate Doped by Alkaline Earth Oxides

NASA Astrophysics Data System (ADS)

Eufrasio, Andreza; Bhatta, Rudra; Pegg, Ian; Dutta, Biprodas

Ceramic oxides are now being considered as a new class of thermoelectric materials because of their high stability at elevated temperatures. Such materials are especially suitable for use as prospective thermoelectric power generators because high temperatures are encountered in such operations. The present investigation uses barium plumbate (BaPbO3) as the starting material, the thermoelectric properties of which have been altered by judicious cation substitutions. BaPbO3 is known to exhibit metallic properties which may turn semiconducting as a result of compositional changes without precipitating a separate phase and/or altering the basic perovskite crystal structure. Perovskite structures are noted for their large interstitial spaces which can accommodate a large variety of ``impurity'' ions. As BaPbO3 has high electrical conductivity, σ = 2.43x105Ω-1 m-1 at room temperature, its thermopower, S, is relatively low, 23 μV/K, as expected. With a thermal conductivity, k, of 4.83Wm-1K-1, the figure of merit (ZT =S2 σ Tk-1) of BaPbO3 is only 0.01 at T = 300K. The objective of this investigation is to study the variation of thermoelectric properties of BaPbO3 as Ba and Pb ions are systematically substituted by alkaline earth ions.

Magnetic Fields of the Earth and Mars a Comparison and Discussion

NASA Technical Reports Server (NTRS)

Taylor, Patrick T.

2004-01-01

In several aspects the magnetic fields of the Earth and Mars are similar but also different. In the past both bodies had planetary magnetic fields but while they Earth's field remains today the Martian ceased to operate, at some unknown time in the past, leaving this planet without a main or core field. This fact resulted in the interaction between the solar and interplanetary magnetic fields with the surfaces of these planets being very different. In addition, Mars has large crustal magnetic anomalies, nearly ten times larger than those on the Earth. Since crustal magnetic anomalies are the product of the thickness of the layer of magnetization, both the magnetizing material and the thickness of the layer of this material must be very different on Mars than Earth. Furthermore, the martian anomalies can only be produced by remanent or fossil magnetization, in contrast with the Earth where both induced and remanent magnetization are producing these anomalies. Crustal magnetic anomalies on the Earth are mainly produced by single-domain, irontitanium oxides, in the form of magnetite being the most common on Mars the main magnetic mineral(s) are unknown. The thickness of the martian magnetized layer in comparison with the Earth remains a major area for research. Determining the paleopole position for the Earth has been done by some of the earliest paleomagnetic researchers. Since we do not have oriented martian rock samples determining the paleopoles for Mars has been done by fitting a magnetization vector to individual magnetic anomalies. Several groups have worked on this problem with somewhat differing results.

Long Life Testing of Oxide-Coated Iridium/Rhenium Rockets

NASA Technical Reports Server (NTRS)

Reed, Brian D.

1995-01-01

22-N class rockets, composed of a rhenium (Re) substrate, an iridium (Ir) coating, and an additional composite coating consisting of Ir and a ceramic oxide, were tested on gaseous oxygen/gaseous hydrogen (GO2/GH2) propellants. Two rockets were tested, one for nearly 39 hours at a nominal mixture ratio (MR) of 4.6 and chamber pressure (Pc) of 469 kPa, and the other for over 13 hours at a nominal MR of 5.8 and 621 kPa Pc. Four additional Ir/Re rockets, with a composite Ir-oxide coating fabricated using a modified process, were also tested, including one for 1.3 hours at a nominal MR of 16.7 and Pc of 503 kPa. The long lifetimes demonstrated on low MR GO2/GH2 suggest greatly extended chamber lifetimes (tens of hours) in the relatively low oxidizing combustion environments of Earth storable propellants. The oxide coatings could also serve as a protective coating in the near injector region, where a still-mixing flowfield may cause degradation of the Ir layer. Operation at MR close to 17 suggests that oxide-coated Ir/Re rockets could be used in severely oxidizing combustion environments, such as high MR GO2/GH2, oxygen/hydrocarbon, and liquid gun propellants.

Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene

NASA Astrophysics Data System (ADS)

Asriza, Ristika O.; Arcana, I. Made

2015-09-01

Cobalt stearate is an oxidant additives that can initiate a process of degradation in high density polyethylene (HDPE). To determine the effect of cobalt stearate in HDPE, oxo-biodegradable polyethylene film was given an irradiation with UV light or heating at various temperature. After given a heating, the FTIR spectra showed a new absorption peak at wave number 1712 cm-1 indicating the presence of carbonyl groups in polymers, whereas after irradiation with UV light is not visible the presence of this absorption peak. The increase concentration of cobalt stearate added in HDPE and the higher heating temperature, the intensity of the absorption peak of the carbonyl group increased. The increasing intensity of the carbonyl group absorption is caused the presence of damage in the film surface after heating, and this result is supported by analysis the surface properties of the film with using SEM. Biodegradation tests were performed on oxo-biodegradable polyethylene film which has been given heating or UV light with using activated sludge under optimal conditions the growth of microorganisms. After biodegradation, the maximum weight decreased by 23% in the oxo-biodegradable polyethylene film with a cobalt stearate concentration of 0.2% and after heating at a temperature of 75 °C for 10 days, and only 0.69% in the same film after irradiation UV light for 10 days. Based on the results above, cobalt stearate additive is more effective to initiate the oxidative degradation of HDPE when it is initiated by heating compared to irradiation with UV light.

Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asriza, Ristika O.; Arcana, I Made, E-mail: arcana@chem.itb.ac.id

Cobalt stearate is an oxidant additives that can initiate a process of degradation in high density polyethylene (HDPE). To determine the effect of cobalt stearate in HDPE, oxo-biodegradable polyethylene film was given an irradiation with UV light or heating at various temperature. After given a heating, the FTIR spectra showed a new absorption peak at wave number 1712 cm{sup −1} indicating the presence of carbonyl groups in polymers, whereas after irradiation with UV light is not visible the presence of this absorption peak. The increase concentration of cobalt stearate added in HDPE and the higher heating temperature, the intensity of themore » absorption peak of the carbonyl group increased. The increasing intensity of the carbonyl group absorption is caused the presence of damage in the film surface after heating, and this result is supported by analysis the surface properties of the film with using SEM. Biodegradation tests were performed on oxo-biodegradable polyethylene film which has been given heating or UV light with using activated sludge under optimal conditions the growth of microorganisms. After biodegradation, the maximum weight decreased by 23% in the oxo-biodegradable polyethylene film with a cobalt stearate concentration of 0.2% and after heating at a temperature of 75 °C for 10 days, and only 0.69% in the same film after irradiation UV light for 10 days. Based on the results above, cobalt stearate additive is more effective to initiate the oxidative degradation of HDPE when it is initiated by heating compared to irradiation with UV light.« less

Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

DOEpatents

Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani

2006-04-04

Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

DOEpatents

Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani; Manivannan, Venkatesan

2004-07-13

Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

Understanding complete oxidation of methane on spinel oxides at a molecular level

DOE PAGES

Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; ...

2015-08-04

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo 2O 4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo 2O 4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo 2Omore » 4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH 3O with a following dehydrogenation to -CH 2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.« less

China's rare-earth industry

USGS Publications Warehouse

Tse, Pui-Kwan

2011-01-01

Introduction China's dominant position as the producer of over 95 percent of the world output of rare-earth minerals and rapid increases in the consumption of rare earths owing to the emergence of new clean-energy and defense-related technologies, combined with China's decisions to restrict exports of rare earths, have resulted in heightened concerns about the future availability of rare earths. As a result, industrial countries such as Japan, the United States, and countries of the European Union face tighter supplies and higher prices for rare earths. This paper briefly reviews China's rare-earth production, consumption, and reserves and the important policies and regulations regarding the production and trade of rare earths, including recently announced export quotas. The 15 lanthanide elements-lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium (atomic numbers 57-71)-were originally known as the rare earths from their occurrence in oxides mixtures. Recently, some researchers have included two other elements-scandium and yttrium-in their discussion of rare earths. Yttrium (atomic number 39), which lies above lanthanum in transition group III of the periodic table and has a similar 3+ ion with a noble gas core, has both atomic and ionic radii similar in size to those of terbium and dysprosium and is generally found in nature with lanthanides. Scandium (atomic number 21) has a smaller ionic radius than yttrium and the lanthanides, and its chemical behavior is intermediate between that of aluminum and the lanthanides. It is found in nature with the lanthanides and yttrium. Rare earths are used widely in high-technology and clean-energy products because they impart special properties of magnetism, luminescence, and strength. Rare earths are also used in weapon systems to obtain the same properties.

Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds.

PubMed

Choi, Jongwook; Choliy, Yuriy; Zhang, Xiawei; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

2009-11-04

(PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH(3))(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and alpha-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

Slip casting and extruding shapes of rhemium with metal oxide additives. Part 2: Development of grain stabilized rhenium parts for resistojets

NASA Technical Reports Server (NTRS)

Barr, Francis A.; Page, Russell J.

1987-01-01

The adaptation of the powdered particle process used for pure metal oxides to the coprocessing of rhenium oxides suitable to produce pure miniature resistojet hardware has been successful. Both slip casting and extrusion processes were used. The metal oxide ZrO2 was stabilized into the cubic phase with Y2O3, for use as a potentially grain stabilizing additive to rhenium. Straight meter long tubing in two sizes are reported. Tubing suitable for resistojet ohmic heater use of fully fired dimensions of nominally 3.8 mm o.d. x 2.2 mm i.d.. and 1.26 mm o.d. x .45 mm i.d. with 0, 0.5, 1.0 and 5.0% zirconia additives were produced for further study. Photomicrographs of these are discussed. The addition of the metal oxide zirconia to rhenium resulted in more dense and less porous parts. The additions of phase stabilized zirconia most likely act as a sintering aid. Tubes of varying diameter were slip cast which were representative of miniature pressure cases.

METHOD OF MAKING ALLOYS OF SECOND RARE EARTH SERIES METALS

DOEpatents

Baker, R.D.; Hayward, B.R.

1963-01-01

>This invention relates to a process for alloying the second rare earth series metals with Mo, Nb, or Zr. A halide of the rare earth metal is mixed with about 1 to 20 at.% of an oxide of Mo, Nb, or Zr. Iodine and an alkali or alkaline earth metal are added, and the resulting mixture is heated in an inert atmosphere to 350 deg C. (AEC)

Mechanisms and modeling of the effects of additives on the nitrogen oxides emission

NASA Technical Reports Server (NTRS)

Kundu, Krishna P.; Nguyen, Hung Lee; Kang, M. Paul

1991-01-01

A theoretical study on the emission of the oxides of nitrogen in the combustion of hydrocarbons is presented. The current understanding of the mechanisms and the rate parameters for gas phase reactions were used to calculate the NO(x) emission. The possible effects of different chemical species on thermal NO(x), on a long time scale were discussed. The mixing of these additives at various stages of combustion were considered and NO(x) concentrations were calculated; effects of temperatures were also considered. The chemicals such as hydrocarbons, H2, CH3OH, NH3, and other nitrogen species were chosen as additives in this discussion. Results of these calculations can be used to evaluate the effects of these additives on the NO(x) emission in the industrial combustion system.

Analysis of Rare Earth Elements in Uranium Using Handheld Laser-Induced Breakdown Spectroscopy (HH LIBS)

DOE PAGES

Manard, Benjamin T.; Wylie, E. Miller; Willson, Stephen P.

2018-05-22

In this paper, a portable handheld laser-induced breakdown spectroscopy (HH LIBS) instrument was evaluated as a rapid method to qualitatively analyze rare earth elements in a uranium oxide matrix. This research is motivated by the need for development of a method to perform rapid, at-line chemical analysis in a nuclear facility, particularly to provide a rapid first pass analysis to determine if additional actions or measurements are warranted. This will result in the minimization of handling and transport of radiological and nuclear material and subsequent exposure to their associated hazards. In this work, rare earth elements (Eu, Nd, and Yb)more » were quantitatively spiked into a uranium oxide powder and analyzed by the HH LIBS instrumentation. This method demonstrates the ability to rapidly identify elemental constituents in sub-percent levels in a uranium matrix. Preliminary limits of detection (LODs) were determined with values on the order of hundredths of a percent. Validity of this methodology was explored by employing a National Institute of Standards and Technology (NIST) standard reference materials (SRM) 610 and 612 (Trace Elements in Glass). Finally, it was determined that the HH LIBS method was able to clearly discern the rare earths elements of interest in the glass or uranium matrices.« less

Analysis of Rare Earth Elements in Uranium Using Handheld Laser-Induced Breakdown Spectroscopy (HH LIBS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manard, Benjamin T.; Wylie, E. Miller; Willson, Stephen P.

In this paper, a portable handheld laser-induced breakdown spectroscopy (HH LIBS) instrument was evaluated as a rapid method to qualitatively analyze rare earth elements in a uranium oxide matrix. This research is motivated by the need for development of a method to perform rapid, at-line chemical analysis in a nuclear facility, particularly to provide a rapid first pass analysis to determine if additional actions or measurements are warranted. This will result in the minimization of handling and transport of radiological and nuclear material and subsequent exposure to their associated hazards. In this work, rare earth elements (Eu, Nd, and Yb)more » were quantitatively spiked into a uranium oxide powder and analyzed by the HH LIBS instrumentation. This method demonstrates the ability to rapidly identify elemental constituents in sub-percent levels in a uranium matrix. Preliminary limits of detection (LODs) were determined with values on the order of hundredths of a percent. Validity of this methodology was explored by employing a National Institute of Standards and Technology (NIST) standard reference materials (SRM) 610 and 612 (Trace Elements in Glass). Finally, it was determined that the HH LIBS method was able to clearly discern the rare earths elements of interest in the glass or uranium matrices.« less

Analysis of Rare Earth Elements in Uranium Using Handheld Laser-Induced Breakdown Spectroscopy (HH LIBS).

PubMed

Manard, Benjamin T; Wylie, E Miller; Willson, Stephen P

2018-01-01

A portable handheld laser-induced breakdown spectroscopy (HH LIBS) instrument was evaluated as a rapid method to qualitatively analyze rare earth elements in a uranium oxide matrix. This research is motivated by the need for development of a method to perform rapid, at-line chemical analysis in a nuclear facility, particularly to provide a rapid first pass analysis to determine if additional actions or measurements are warranted. This will result in the minimization of handling and transport of radiological and nuclear material and subsequent exposure to their associated hazards. In this work, rare earth elements (Eu, Nd, and Yb) were quantitatively spiked into a uranium oxide powder and analyzed by the HH LIBS instrumentation. This method demonstrates the ability to rapidly identify elemental constituents in sub-percent levels in a uranium matrix. Preliminary limits of detection (LODs) were determined with values on the order of hundredths of a percent. Validity of this methodology was explored by employing a National Institute of Standards and Technology (NIST) standard reference materials (SRM) 610 and 612 (Trace Elements in Glass). It was determined that the HH LIBS method was able to clearly discern the rare earths elements of interest in the glass or uranium matrices.

Origin and evolution of the atmospheres of early Venus, Earth and Mars

NASA Astrophysics Data System (ADS)

Lammer, Helmut; Zerkle, Aubrey L.; Gebauer, Stefanie; Tosi, Nicola; Noack, Lena; Scherf, Manuel; Pilat-Lohinger, Elke; Güdel, Manuel; Grenfell, John Lee; Godolt, Mareike; Nikolaou, Athanasia

2018-05-01

We review the origin and evolution of the atmospheres of Earth, Venus and Mars from the time when their accreting bodies were released from the protoplanetary disk a few million years after the origin of the Sun. If the accreting planetary cores reached masses ≥ 0.5 M_Earth before the gas in the disk disappeared, primordial atmospheres consisting mainly of H_2 form around the young planetary body, contrary to late-stage planet formation, where terrestrial planets accrete material after the nebula phase of the disk. The differences between these two scenarios are explored by investigating non-radiogenic atmospheric noble gas isotope anomalies observed on the three terrestrial planets. The role of the young Sun's more efficient EUV radiation and of the plasma environment into the escape of early atmospheres is also addressed. We discuss the catastrophic outgassing of volatiles and the formation and cooling of steam atmospheres after the solidification of magma oceans and we describe the geochemical evidence for additional delivery of volatile-rich chondritic materials during the main stages of terrestrial planet formation. The evolution scenario of early Earth is then compared with the atmospheric evolution of planets where no active plate tectonics emerged like on Venus and Mars. We look at the diversity between early Earth, Venus and Mars, which is found to be related to their differing geochemical, geodynamical and geophysical conditions, including plate tectonics, crust and mantle oxidation processes and their involvement in degassing processes of secondary N_2 atmospheres. The buildup of atmospheric N_2, O_2, and the role of greenhouse gases such as CO_2 and CH_4 to counter the Faint Young Sun Paradox (FYSP), when the earliest life forms on Earth originated until the Great Oxidation Event ≈ 2.3 Gyr ago, are addressed. This review concludes with a discussion on the implications of understanding Earth's geophysical and related atmospheric evolution in relation

Protection against oxidation of fish-oil-enriched milk emulsions through addition of rapeseed oil or antioxidants.

PubMed

Let, Mette B; Jacobsen, Charlotte; Pham, Kim A; Meyer, Anne S

2005-06-29

The ability of rapeseed oil and/or different antioxidants (alpha- and gamma-tocopherol mixture, ascorbyl palmitate, and EDTA) to protect fish-oil-enriched milk emulsions against oxidation was investigated. Tocopherol isomers in concentrations similar to those found in natural rapeseed oil were added to rapeseed oil stripped of natural tocopherols. The rapeseed oil with added tocopherols significantly inhibited oxidation in the fish-oil-enriched milk emulsions. In contrast, the emulsions with only fish oil and added alpha- and gamma-tocopherol were less stable than the emulsions with fish oil alone. When added individually, the gamma-tocopherol seemed to inhibit oxidation more efficiently than alpha-tocopherol. Ascorbyl palmitate (AP) almost completely retarded oxidation in the fish-oil-enriched milk emulsions, as determined by PV, volatile oxidation products, and sensory evaluation. AP also prevented the otherwise prooxidant effect of tocopherols added to fish oil before emulsification. No interactions between AP, tocopherols, and EDTA were observed, and EDTA added alone to fish oil did not show antioxidant properties in the milk emulsions. Overall, the results showed that addition of AP or rapeseed oil containing natural tocopherols to fish oil was equally efficient in inhibiting oxidation in the fish-oil-enriched milk emulsions.

Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands

DOE PAGES

Fester, J.; García-Melchor, M.; Walton, A. S.; ...

2017-01-30

Here, transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress in the development of highly active oxide nanostructures is hampered by a lack of knowledge of the location and nature of the active sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy and computational modelling, how hydroxyls form from water dissociation at under coordinated cobalt edge sites of cobalt oxide nanoislands. Surprisingly, we find that an additional water molecule acts to promote all the elementary steps of the dissociation process and subsequent hydrogen migration, revealing the importantmore » assisting role of a water molecule in its own dissociation process on a metal oxide. Inspired by the experimental findings, we theoretically model the oxygen evolution reaction activity of cobalt oxide nanoislands and show that the nanoparticle metal edges also display favourable adsorption energetics for water oxidation under electrochemical conditions.« less

Separation of the rare-earth fission product poisons from spent nuclear fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christian, Jerry D.; Sterbentz, James W.

A method for the separation of the rare-earth fission product poisons comprising providing a spent nuclear fuel. The spent nuclear fuel comprises UO.sub.2 and rare-earth oxides, preferably Sm, Gd, Nd, Eu oxides, with other elements depending on the fuel composition. Preferably, the provided nuclear fuel is a powder, preferably formed by crushing the nuclear fuel or using one or more oxidation-reduction cycles. A compound comprising Th or Zr, preferably metal, is provided. The provided nuclear fuel is mixed with the Th or Zr, thereby creating a mixture. The mixture is then heated to a temperature sufficient to reduce the UO.sub.2more » in the nuclear fuel, preferably to at least to 850.degree. C. for Th and up to 600.degree. C. for Zr. Rare-earth metals are then extracted to form the heated mixture thereby producing a treated nuclear fuel. The treated nuclear fuel comprises the provided nuclear fuel having a significant reduction in rare-earths.« less

Effect of H2O on metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe: Implications for the oxidation state of the Earth and Mars

NASA Astrophysics Data System (ADS)

Clesi, V.; Bouhifd, M. A.; Bolfan-Casanova, N.; Manthilake, G.; Fabbrizio, A.; Andrault, D.

2016-11-01

This study investigates the metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe during core mantle differentiation of terrestrial planets under hydrous conditions. For this, we equilibrated a molten hydrous CI chondrite model composition with various Fe-rich alloys in the system Fe-C-Ni-Co-Si-S in a multi-anvil over a range of P, T, fO2 and water content (5-20 GPa, 2073-2500 K, from 1 to 5 log units below the iron-wüstite (IW) buffer and for XH2O varying from 500 ppm to 1.5 wt%). By comparing the present experiments with the available data sets on dry systems, we observes that the effect of water on the partition coefficients of moderately siderophile elements is only moderate. For example, for iron we observed a decrease in the partition coefficient of Fe (Dmet/silFe) from 9.5 to 4.3, with increasing water content of the silicate melt, from 0 to 1.44 wt%, respectively. The evolution of metal-silicate partition coefficients of Ni, Co, V, Cr, Mn and Fe are modelled based on sets of empirical parameters. These empirical models are then used to refine the process of core segregation during accretion of Mars and the Earth. It appears that the likely presence of 3.5 wt% water on Mars during the core-mantle segregation could account for ∼74% of the FeO content of the Martian mantle. In contrast, water does not play such an important role for the Earth; only 4-6% of the FeO content of its mantle could be due to the water-induced Fe-oxidation, for a likely initial water concentration of 1.8 wt%. Thus, in order to reproduce the present-day FeO content of 8 wt% in the mantle, the Earth could initially have been accreted from a large fraction (between 85% and 90%) of reducing bodies (similar to EH chondrites), with 10-15% of the Earth's mass likely made of more oxidized components that introduced the major part of water and FeO to the Earth. This high proportion of enstatite chondrites in the original constitution of the Earth is consistent with the 17O,48Ca,50Ti,62Ni

Biodegradation of organic matter and anodic microbial communities analysis in sediment microbial fuel cells with/without Fe(III) oxide addition.

PubMed

Xu, Xun; Zhao, Qingliang; Wu, Mingsong; Ding, Jing; Zhang, Weixian

2017-02-01

To enhance the biodegradation of organic matter in sediment microbial fuel cell (SMFC), Fe(III) oxide, as an alternative electron acceptor, was added into the sediment. Results showed that the SMFC with Fe(III) oxide addition obtained higher removal efficiencies for organics than the SMFC without Fe(III) oxide addition and open circuit bioreactor, and produced a maximum power density (P max ) of 87.85mW/m 2 with a corresponding maximum voltage (V max ) of 0.664V. The alteration of UV-254 and specific ultraviolet absorbance (SUVA) also demonstrated the organic matter in sediments can be effectively removed. High-throughput sequencing of anodic microbial communities indicated that bacteria from the genus Geobacter were predominantly detected (21.23%) in the biofilm formed on the anode of SMFCs, while Pseudomonas was the most predominant genus (18.12%) in the presence of Fe(III) oxide. Additionally, compared with the open circuit bioreactor, more electrogenic bacteria attached to the biofilm of anode in SMFCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Aryl Ketone Synthesis via Tandem Orthoplatinated Triarylphosphite-Catalyzed Addition Reactions of Arylboronic Acids with Aldehydes Followed by Oxidation

PubMed Central

Liao, Yuan-Xi; Hu, Qiao-Sheng

2010-01-01

Tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

Folate receptor targeted, rare-earth oxide nanocrystals for bi-modal fluorescence and magnetic imaging of cancer cells.

PubMed

Setua, Sonali; Menon, Deepthy; Asok, Adersh; Nair, Shantikumar; Koyakutty, Manzoor

2010-02-01

Targeted cancer imaging using rare-earth oxide nanocrystals, free from heavy metals (Cd, Se, Te, Hg and Pb), showing bright red-fluorescence and magnetic resonance imaging (MRI) is presented. Y(2)O(3) nanocrystals (YO NC) doped in situ with fluorescent (Eu(3+)) and paramagnetic (Gd(3+)) impurities and conjugated with a potential cancer targeting ligand, folic acid (FA), were prepared using an all-aqueous wet-chemical process. Structural, optical and magnetic properties of these multifunctional nanocrystals were investigated by X-ray diffraction, electron microscopy, photoluminescence and magnetization studies. Highly monodisperse nanocrystals of size approximately 20 nm with cubic bixbyite crystal structure showed bright red-fluorescence when doped with Eu(3+). Co-doping with Gd(3+) and mild air drying resulted significantly enhanced fluorescence quantum efficiency of approximately 60% together with paramagnetic functionality, enabling T(1)-weighted MR contrast with approximately 5 times higher spin-lattice relaxivity compared to the clinically used Gd(3+) contrast agent. Cytotoxicity and reactive oxygen stress studies show no toxicity by YO NC in both normal and cancer cells up to higher doses of 500 microm and longer incubation time, 48h. Cancer targeting capability of FA conjugated NCs was demonstrated on folate receptor positive (FR+) human nasopharyngeal carcinoma cells (KB) with FR depressed KB (FRd) and FR negative (FR-) lung cancer cells A549 as controls. Fluorescence microscopy and flow-cytometry data show highly specific binding and cellular uptake of large concentration of FA conjugated NCs on FR+ve cells compared to the controls. Thus, the present study reveals, unique bi-modal contrast imaging capability, non-toxicity and cancer targeting capability of multiple impurities doped rare-earth oxide nanocrystals that can find promising application in molecular imaging.

Organic Aerosols in the Presence of CO{sub 2} in the Early Earth and Exoplanets: UV–Vis Refractive Indices of Oxidized Tholins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavilan, Lisseth; Carrasco, Nathalie; Vettier, Ludovic

In this experimental study we investigate the role of atmospheric CO{sub 2} on the optical properties of organic photochemical aerosols. To this end, we add CO{sub 2} to a N{sub 2}:CH{sub 4} gas mixture used in a plasma typically used for Titan studies. We produce organic thin films (tholins) in plasmas where the CO{sub 2}/CH{sub 4} ratio is increased from 0 to 4. We measure these films via spectrometric ellipsometry and apply a Tauc–Lorentz model, used for optically transparent materials, to obtain the thickness of the thin film, its optical band gap, and the refractive indices in the UV–visible (270–600more » nm). All samples present a significant absorption band in the UV. According to the Tauc–Lorentz model, as the CO{sub 2}/CH{sub 4} ratio is quadrupled, the position of the UV band is shifted from ∼177 nm to 264 nm while its strength is quadrupled. Consequently, we infer that oxidized organic aerosols absorb more efficiently at longer UV wavelengths than reduced aerosols. Our laboratory wavelength-tabulated UV–vis refractive indices provide new constraints to atmospheric models of the early Earth and Earth-like exoplanets including photochemical hazes formed under increasingly oxidizing conditions.« less

Stoichiometry and kinetics of the anaerobic ammonium oxidation (Anammox) with trace hydrazine addition.

PubMed

Yao, Zongbao; Lu, Peili; Zhang, Daijun; Wan, Xinyu; Li, Yulian; Peng, Shuchan

2015-12-01

Purpose of this study is to investigate the stoichiometry and kinetics of anaerobic ammonium oxidation (Anammox) with trace hydrazine addition. The stoichiometry was established based on the electron balance of Anammox process with trace N2H4 addition. The stoichiometric coefficients were determined by the proton consumption and the changes in substrates and products. It was found that trace N2H4 addition can increase the yield of Anammox bacteria (AnAOB) and reduce NO3(-) yield, which enhances the Anammox. Subsequently, kinetic model of Anammox with trace N2H4 addition was developed, and the parameters of the anaerobic degradation model of N2H4 were obtained for the first time. The maximum specific substrate utilization rate, half-saturation constant and inhibition constant of N2H4 were 25.09mgN/g VSS/d, 10.42mgN/L and 1393.88mgN/L, respectively. These kinetic parameters might provide important information for the engineering applications of Anammox with trace N2H4 addition. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interplay between solid Earth and biological evolution

NASA Astrophysics Data System (ADS)

Höning, Dennis; Spohn, Tilman

2017-04-01

Major shifts in Earth's evolution led to progressive adaptations of the biosphere. Particularly the emergence of continents permitted efficient use of solar energy. However, the widespread evolution of the biosphere fed back to the Earth system, often argued as a cause for the great oxidation event or as an important component in stabilizing Earth's climate. Furthermore, biologically enhanced weathering rates alter the flux of sediments in subduction zones, establishing a potential link to the deep interior. Stably bound water within subducting sediments not only enhances partial melting but further affects the mantle rheology. The mantle responds by enhancing its rates of convection, water outgassing, and subduction. How crucial is the emergence and evolution of life on Earth to these processes, and how would Earth have been evolved without the emergence of life? We here discuss concepts and present models addressing these questions and discuss the biosphere as a major component in evolving Earth system feedback cycles.

Vacuum distillation of a mixture of LiCl-KCl eutectic salts and RE oxidative precipitates and a dechlorination and oxidation of RE oxychlorides.

PubMed

Eun, Hee Chul; Yang, Hee Chul; Cho, Yung Zun; Lee, Han Soo; Kim, In Tae

2008-12-30

In this study, a vacuum distillation of a mixture of LiCl-KCl eutectic salt and rare-earth oxidative precipitates was performed to separate a pure LiCl-KCl eutectic salt from the mixture. Also, a dechlorination and oxidation of the rare-earth oxychlorides was carried out to stabilize a final waste form. The mixture was distilled under a range of 710-759.5Torr of a reduced pressure at a fixed heating rate of 4 degrees C/min and the LiCl-KCl eutectic salt was completely separated from the mixture. The required time for the salt distillation and the starting temperature for the salt vaporization were lowered with a reduction in the pressure. Dechlorination and oxidation of the rare-earth oxychlorides was completed at a temperature below 1300 degrees C and this was dependent on the partial pressure of O2. The rare-earth oxychlorides (NdOCl/PrOCl) were transformed to oxides (Nd2O3/PrO2) during the dechlorination and oxidation process. These results will be utilized to design a concept for a process for recycling the waste salt from an electrorefining process.

Energetics of alkali and alkaline earth ion-exchanged zeolite A

DOE PAGES

Sun, Hui; Wu, Di; Liu, Kefeng; ...

2016-06-30

Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential ( Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO 2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A)more » to –48.02 ± 1.85 kJ/mol per TO 2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO 2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.« less

Comparison of reactivity of Pt(II) center in the mononuclear and binuclear organometallic diimineplatinum complexes toward oxidative addition of methyl iodide

NASA Astrophysics Data System (ADS)

Hashemi, Majid

2016-01-01

The reactivities of Pt(II) center in a series of organometallic mononuclear Pt(II), binuclear Pt(II) and binuclear mixed-valence Pt(II)-Pt(IV) complexes toward oxidative addition of MeI have been compared from a theoretical point of view. The nucleophilicity index and electron-donation power were calculated for each of these complexes. The energies of HOMO and dZ2 orbital were determined for these complexes. Very good correlations were found between logk2 (k2 is the experimentally determined second order rate constant for the oxidative addition of MeI on these complexes) and nucleophilicity index or electron-donation power for these complexes. The correlation between logk2 and the energy of HOMO or the energy of dZ2 orbital were also very good. The condensed-to-atom Fukui functions for electrophilic attack on these complexes showed that the Pt(II) center is the preferred site for the oxidative addition of MeI. All of these observations are in agreement with the proposed SN2 type mechanism in the oxidative addition of MeI on the Pt(II) center in these complexes.

Ion beam sputter-deposited thin film coatings for protection of spacecraft polymers in low Earth orbit

NASA Technical Reports Server (NTRS)

Banks, B. A.; Mirtich, M. J.; Rutledge, S. K.; Swec, D. M.; Nahra, H. K.

1985-01-01

Ion beam sputter-deposited thin films of Al2O3, SiO2, and a codeposited mixture of predominantly SiO2 with small amounts of a fluoropolymer were evaluated both in laboratory plasma ashing tests and in space on board shuttle flight STS-8 for effectiveness in preventing oxidation of polyimide Kapton. Measurements of mass loss and optical performance of coated and uncoated polyimide samples exposed to the low Earth orbital environment are presented. Optical techniques were used to measure loss rates of protective films exposed to atomic oxygen. Results of the analysis of the space flight exposed samples indicate that thin film metal oxide coatings are very effective in protecting the polyimide. Metal oxide coatings with a small amount of fluoropolymer codeposited have the additional benefit of great flexibility.

Ion beam sputter-deposited thin film coatings for protection of spacecraft polymers in low earth orbit

NASA Technical Reports Server (NTRS)

Banks, B. A.; Mirtich, M. J.; Rutledge, S. K.; Swec, D. M.; Nahra, H. K.

1985-01-01

Ion beam sputter-deposited thin films at Al2O3, SiO2, and a codeposited mixture of predominantly SiO2 with small amounts of fluoropolymer were evaluated both in laboratory plasma ashing tests and in space on board Shuttle flight STS-8 for effectiveness in preventing oxidation of polyimide Kapton. Measurements of mass loss and optical performance of coated and uncoated polyimide samples exposed to the low earth orbital environment are presented. Optical techniques were used to measure loss rates of protective films exposed to atomic oxygen. Results of the analysis of the space flight exposed samples indicate that thin film metal oxide coatings are very effective in protecting the polyimide. Metal oxide coatings with a small amount of fluoropolymer codeposited have the additional benefit of great flexibility.

Effect of LEO Exposure on Aromatic Polymers Containing Phenylphosphine Oxide Groups

NASA Technical Reports Server (NTRS)

Watson, K. A.; Ghose, S.; Lillehei, P. T.; Smith, J. G., Jr.; Connell, J. W.

2007-01-01

As part of the Materials on The International Space Station Experiment (MISSE), aromatic polymers containing phenylphosphine oxide groups were exposed to low Earth orbit (LEO) for approximately 4 years. All of the aromatic polymers containing phenylphosphine oxide groups survived the exposure despite the high fluence of atomic oxygen that completely eroded other polymer films such as Kapton and Mylar of comparable or greater thickness. The samples consisted of a colorless polyimide film and a poly(arylene ether benzimidazole) film and thread. The samples were characterized for changes in physical properties, thermal/optical properties (i.e. solar absorptivity and thermal emissivity), surface chemistry (X-ray photoelectron spectroscopy), and surface topography (atomic force microscopy). The data from the polymer samples on MISSE were compared to samples from the same batch of material stored under ambient conditions on Earth. In addition, comparisons were made between the MISSE samples and those subjected to shorter term space flight exposures. The results of these analyses will be presented.

Furnace Cyclic Behavior of Plasma-Sprayed Zirconia-Yttria and Multi-Component Rare Earth Oxide Doped Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Nesbitt, James A.; McCue, Terry R.; Barrett, Charles A.; Miller, Robert A.

2002-01-01

Ceramic thermal barrier coatings will play an increasingly important role in advanced gas turbine engines because of their ability to enable further increases in engine temperatures. However, the coating performance and durability become a major concern under the increasingly harsh thermal cycling conditions. Advanced zirconia- and hafnia-based cluster oxide thermal barrier coatings with lower thermal conductivity and improved thermal stability are being developed using a high-heat-flux laser-rig based test approach. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of numerous candidate coating materials was carried out using conventional furnace cyclic tests. In this paper, furnace thermal cyclic behavior of the advanced plasma-sprayed zirconia-yttria-based thermal barrier coatings that were co-doped with multi-component rare earth oxides was investigated at 1163 C using 45 min hot cycles. The ceramic coating failure mechanisms were studied by using scanning electron microscopy combined with X-ray diffraction phase analysis after the furnace tests. The coating cyclic lifetime will be discussed in relation to coating phase structures, total dopant concentrations, and other properties.

Low temperature synthesis of LnOF rare-earth oxyfluorides through reaction of the oxides with PTFE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutton, S.E., E-mail: sdutton@princeton.edu; Hirai, D.; Cava, R.J.

2012-03-15

Highlights: Black-Right-Pointing-Pointer Low temperature synthesis of LnOF rare-earth oxyfluorides from Ln{sub 2}O{sub 3} and PTFE (CF{sub 2}). Black-Right-Pointing-Pointer Rhombohedral LnOF is the major phase and forms as nanocrystals, 29-103 nm. Black-Right-Pointing-Pointer Expected lanthanide contraction observed in lattice parameters and bond lengths. Black-Right-Pointing-Pointer TbOF orders antiferromagnetically at 10 K and has a metamagnetic transition at 1.8 T. Black-Right-Pointing-Pointer GdOF orders antiferromagnetically at 5 K, other LnOF are paramagnetic. -- Abstract: A low temperature solid-state synthesis route, employing polytetrafluoroethylene (PTFE) and the rare-earth oxides, for the formation of the LnOF rare-earth oxyfluorides (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb,more » Dy, Ho, Er), is reported. With the exception of LaOF, which forms in a tetragonal variant, rhomobohedral LnOF is found to be the major product of the reaction. In the case of PrOF, a transition from the rhombohedral to the cubic fluorite phase is observed on heating in air to 500 Degree-Sign C. X-ray diffraction shows the expected lanthanide contraction in the lattice parameters and bond lengths. Magnetic susceptibility measurements show antiferromagnetic-like ordering in TbOF, T{sub m} = 10 K, with a metamagnetic transition at a field {mu}{sub 0}H{sub t} = 1.8 T at 2 K. An antiferromagnetic transition, T{sub N} = 4 K, is observed in GdOF. Paramagnetic behavior is observed above 2 K in PrOF, NdOF, DyOF, HoOF and ErOF. The magnetic susceptibility of EuOF is characteristic of Van Vleck paramagnetism.« less

MnFe2O4-graphene oxide magnetic nanoparticles as a high-performance adsorbent for rare earth elements: Synthesis, isotherms, kinetics, thermodynamics and desorption.

PubMed

Ghobadi, Misagh; Gharabaghi, Mahdi; Abdollahi, Hadi; Boroumand, Zohreh; Moradian, Marzieh

2018-06-05

In recent decades, considerable amounts of rare earth elements have been used and then released into industrial wastewater, which caused serious environmental problems. In this work, in order to recycle rare earth cations (La 3+ and Ce 3+ ) from aqueous solutions, MnFe 2 O 4 -Graphene oxide magnetic nanoparticles were synthesized and after characterization studies, their adsorption isotherms, kinetics, thermodynamics and desorption were comprehensively investigated. Characterized was performed using XRD, FE-SEM, FT-IR, Raman spectroscopy, VSM, BET and DLS. REE adsorption on MnFe 2 O 4 -GO was studied for the first time in the present work and the maximum adsorption capacity at the optimum condition (room temperature and pH = 7) for La 3+ and Ce 3+ were 1001 and 982 mg/g respectively, and the reactions were completed within 20 min. In addition, the adsorption data were well matched with the Langmuir model and the adsorption kinetics were fitted with the pseudo-second order model. The thermodynamic parameters were calculated and the reactions were found to be endothermic and spontaneous. Moreover, the Dubinin-Radushkevich model predicted chemical ion-exchange adsorption. Desorption studies also demonstrated that MnFe 2 O 4 -GO can be regenerated for multiple reuses. Overall, high adsorption capacity, chemical stability, reusability, fast kinetics, easy magnetic separation, and simple synthesis method indicated that MnFe 2 O 4 -GO is a high-performance adsorbent for REE. Copyright © 2018. Published by Elsevier B.V.

Effect of Cr2O3 addition on the oxidation induration mechanism of Hongge vanadium titanomagnetite pellets

NASA Astrophysics Data System (ADS)

Li, Wei; Wang, Nan; Fu, Gui-qin; Chu, Man-sheng; Zhu, Miao-yong

2018-04-01

As part of a research project to develop a novel clean smelting process for the comprehensive utilization of Hongge vanadium titanomagnetite (HVTM), in this study, the effect of Cr2O3 addition on the oxidation induration mechanism of HVTM pellets (HVTMPs) was investigated in detail. The results showed that the compressive strength of the HVTMPs was greatly weakened by the Cr2O3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr2O3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr2O3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe-Cr solid solutions (Fe1.2Cr0.8O3 and Fe0.7Cr1.3O3) embedded in the hematite grains. Moreover, the compact hematite was destroyed by forming a dispersed structure and the hematite recrystallization was hindered during the oxidation induration, which adversely affected the compressive strength. On the basis of these results, a schematic was formulated to describe the oxidation induration mechanism with different amounts of added Cr2O3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.

Earth Science Europe "Is Earth Science Europe an interesting and useful construct?"

NASA Astrophysics Data System (ADS)

Ludden, John

2015-04-01

In 2014 we managed to have a group of earth scientists from across the spectrum: from academic, survey, industry and government, pull together to create the first output for Earth Science Europe http://www.bgs.ac.uk/earthScienceEurope/downloads/EarthScienceEuropeBrochure.pdf In this document we stated that Earth scientists need a united, authoritative voice to enhance the status and impact of Earth science across Europe. The feeling was that there were many diverse infrastructure and research initiatives spanning the terrestrial and oceanic realms and science ranged from historical geology to active dynamics on Earth, and that a level of coordination and mutual knowledge sharing was necessary. In addition to a better understanding of the Earth in general, we thought there was a need to have Earth Science Europe develop a strategic research capacity in geohazards, georesources and environmental earth sciences, through a roadmap addressing fundamental and societal challenges. This would involve a robust research infrastructure to deliver strategic goals, enabling inspirational research and promoting solutions to societal challenges. In this talk I will propose some next steps and discuss what this "authoritative voice" could look like and ask the question - "is Earth Science Europe and interesting and useful concept?"

Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

2016-12-01

Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be

Haze aerosols in the atmosphere of early Earth: manna from heaven.

PubMed

Trainer, Melissa G; Pavlov, Alexander A; Curtis, Daniel B; McKay, Christopher P; Worsnop, Douglas R; Delia, Alice E; Toohey, Darin W; Toon, Owen B; Tolbert, Margaret A

2004-01-01

An organic haze layer in the upper atmosphere of Titan plays a crucial role in the atmospheric composition and climate of that moon. Such a haze layer may also have existed on the early Earth, providing an ultraviolet shield for greenhouse gases needed to warm the planet enough for life to arise and evolve. Despite the implications of such a haze layer, little is known about the organic material produced under early Earth conditions when both CO(2) and CH(4) may have been abundant in the atmosphere. For the first time, we experimentally demonstrate that organic haze can be generated in different CH(4)/CO(2) ratios. Here, we show that haze aerosols are able to form at CH(4) mixing ratios of 1,000 ppmv, a level likely to be present on early Earth. In addition, we find that organic hazes will form at C/O ratios as low as 0.6, which is lower than the predicted value of unity. We also show that as the C/O ratio decreases, the organic particles produced are more oxidized and contain biologically labile compounds. After life arose, the haze may thus have provided food for biota.

Abiotic production of nitrous oxide by lightning. Implications for a false positive identification of life on Earth-Like Planets around quiescent M Dwarfs

NASA Astrophysics Data System (ADS)

Navarro, Karina F.; Navarro-Gonzalez, Rafael; McKay, Christopher P.

Nitrous oxide (N _{2}O) is uniformly mixed in the troposphere with a concentration of about 310 ppb but disappears in the stratosphere (Prinn et al., 1990); N _{2}O is mostly emitted at a rate of 1x10 (13) g yr (-1) as a byproduct of microbial activity in soils and in the ocean by two processes: a) denitrification (reduction of nitrate and nitrite), and b) nitrification (oxidation of ammonia) (Maag and Vinther, 1996). The abiotic emission of N _{2}O in the contemporaneous Earth is small, mostly arising from lightning activity (2x10 (9) g yr (-1) , Hill et al., 1984) and by reduction of nitrite by Fe(II)-minerals in soils in Antarctica (Samarkin et al., 2010). Since N _{2}O has absorption bands in the mid-IR (7.8, 8.5, and 17 mumm) that makes it detectable by remote sensing (Topfer et al., 1997; Des Marais et al., 2002), it has been suggested as a potential biosignature in the search for life in extrasolar planets (Churchill and Kasting, 2000). However, the minimum required concentration for positive identification is 10,000 ppb with missions like Terrestrial Planet Finder and Darwin (Churchill and Kasting, 2000). Therefore, it is not a suitable biomarker for extrasolar Earth-like planets orbiting stars similar to the Sun. Because N _{2}O is protected in the troposphere from UV photolysis by the stratospheric ozone layer, its concentration would decrease with decreasing oxygen (O _{2}) concentrations, if the biological source strength remains constant (Kasting and Donahue, 1980). For a primitive Earth-like (Hadean) atmosphere dominated by CO _{2}, and no free O _{2}, the expected N _{2}O concentration would be about 3 ppb with the current microbial N _{2}O flux (Churchill and Kasting, 2000). The resulting N _{2}O spectral signature of this atmosphere would be undetectable unless the N _{2}O microbial flux would be 10 (4) greater than its present value (Churchill and Kasting, 2000). Since this flux is unlikely, it is impossible to use it as a biomarker in anoxic CO

Selective Emitter Pumped Rare Earth Laser

NASA Technical Reports Server (NTRS)

Chubb, Donald L. (Inventor); Patton, Martin O. (Inventor)

2001-01-01

A selective emitter pumped rare earth laser provides an additional type of laser for use in many laser applications. Rare earth doped lasers exist which are pumped with flashtubes or laser diodes. The invention uses a rare earth emitter to transform thermal energy input to a spectral band matching the absorption band of a rare earth in the laser in order to produce lasing.

Self-propagating high-temperature synthesis and luminescent properties of ytterbium doped rare earth (Y, Sc, Lu) oxides nanopowders

NASA Astrophysics Data System (ADS)

Permin, D. A.; Novikova, A. V.; Balabanov, S. S.; Gavrishchuk, E. M.; Kurashkin, S. V.; Savikin, A. P.

2018-04-01

This paper describes a comparative study of structural and luminescent properties of 5%Yb-doped yttrium, scandium, and lutetium oxides (Yb:RE2O3) powders and ceramics fabricated by self-propagating high-temperature synthesis. According to X-ray diffractometry and electron microscopy the chosen method ensures preparation of low-agglomerated cubic Ctype crystal structured powders at one step. No crucial differences in luminescence spectra were found the Yb:RE2O3 powders and ceramics. It was shown that the emission lifetimes of the Yb:RE2O3 powders are lowered by crystal structure defects, while its values for ceramics samples are compared to that of monocrystals and more influenced by rare earth impurities.

Enantioselective synthesis of substituted piperidines by addition of aryl Grignard reagents to pyridine N-oxides.

PubMed

Hussain, Munawar; Banchelin, Thomas Sainte-Luce; Andersson, Hans; Olsson, Roger; Almqvist, Fredrik

2013-01-04

The synthesis of optically active piperidines by enantioselective addition of aryl Grignard reagents to pyridine N-oxides and lithium binolate followed by reduction is reported for the first time. The reaction results in high yields (51-94%) in combination with good ee (54-80%). Some of these products were subsequently recrystallized, affording enhanced optical purities (>99% ee).

Synthesis of a Fluorescent Acridone Using a Grignard Addition, Oxidation, and Nucleophilic Aromatic Substitution Reaction Sequence

ERIC Educational Resources Information Center

Goodrich, Samuel; Patel, Miloni; Woydziak, Zachary R.

2015-01-01

A three-pot synthesis oriented for an undergraduate organic chemistry laboratory was developed to construct a fluorescent acridone molecule. This laboratory experiment utilizes Grignard addition to an aldehyde, alcohol oxidation, and iterative nucleophilic aromatic substitution steps to produce the final product. Each of the intermediates and the…

Additional oxidative stress reroutes the global response of Aspergillus fumigatus to iron depletion.

PubMed

Kurucz, Vivien; Krüger, Thomas; Antal, Károly; Dietl, Anna-Maria; Haas, Hubertus; Pócsi, István; Kniemeyer, Olaf; Emri, Tamás

2018-05-10

Aspergillus fumigatus has to cope with a combination of several stress types while colonizing the human body. A functional interplay between these different stress responses can increase the chances of survival for this opportunistic human pathogen during the invasion of its host. In this study, we shed light on how the H 2 O 2 -induced oxidative stress response depends on the iron available to this filamentous fungus, using transcriptomic analysis, proteomic profiles, and growth assays. The applied H 2 O 2 treatment, which induced only a negligible stress response in iron-replete cultures, deleteriously affected the fungus under iron deprivation. The majority of stress-induced changes in gene and protein expression was not predictable from data coming from individual stress exposure and was only characteristic for the combination of oxidative stress plus iron deprivation. Our experimental data suggest that the physiological effects of combined stresses and the survival of the fungus highly depend on fragile balances between economization of iron and production of essential iron-containing proteins. One observed strategy was the overproduction of iron-independent antioxidant proteins to combat oxidative stress during iron deprivation, e.g. the upregulation of superoxide dismutase Sod1, the thioredoxin reductase Trr1, and the thioredoxin orthologue Afu5g11320. On the other hand, oxidative stress induction overruled iron deprivation-mediated repression of several genes. In agreement with the gene expression data, growth studies underlined that in A. fumigatus iron deprivation aggravates oxidative stress susceptibility. Our data demonstrate that studying stress responses under separate single stress conditions is not sufficient to understand how A. fumigatus adapts in a complex and hostile habitat like the human body. The combinatorial stress of iron depletion and hydrogen peroxide caused clear non-additive effects upon the stress response of A. fumigatus. Our data

Recycling of LiCl-KCl eutectic based salt wastes containing radioactive rare earth oxychlorides or oxides

NASA Astrophysics Data System (ADS)

Eun, H. C.; Cho, Y. Z.; Son, S. M.; Lee, T. K.; Yang, H. C.; Kim, I. T.; Lee, H. S.

2012-01-01

Recycling of LiCl-KCl eutectic salt wastes containing radioactive rare earth oxychlorides or oxides was studied to recover renewable salts from the salt wastes and to minimize the radioactive wastes by using a vacuum distillation method. Vaporization of the LiCl-KCl eutectic salt was effective above 900 °C and at 5 Torr. The condensations of the vaporized salt were largely dependent on temperature gradient. Based on these results, a recycling system of the salt wastes as a closed loop type was developed to obtain a high efficiency of the salt recovery condition. In this system, it was confirmed that renewable salt was recovered at more than 99 wt.% from the salt wastes, and the changes in temperature and pressure in the system could be utilized to understand the present condition of the system operation.

Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

PubMed

Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

2015-08-18

The search for new catalysts for more efficient, selective chemical transformations and for the synthesis of new functional materials has been a long-standing research subject in both academia and industry. To develop new generations of catalysts that are superior or complementary to the existing ones, exploring the potential of untapped elements is an important strategy. Rare-earth elements, including scandium, yttrium, and the lanthanides (La-Lu), constitute one important frontier in the periodic table. Rare-earth elements possess unique chemical and physical properties that are different from those of main-group and late-transition metals. The development of rare-earth-based catalysts by taking the advantage of these unique properties is of great interest and importance. The most stable oxidation state of rare-earth metals is 3+, which is difficult to change under many reaction conditions. The oxidative addition and reductive elimination processes often observed in catalytic cycles involving late transition metals are generally difficult in the case of rare-earth complexes. The 18-electron rule that is applicable to late-transition-metal complexes does not fit rare-earth complexes, whose structures are mainly governed by the sterics (rather than the electron numbers) of the ligands. In the lanthanide series (La-Lu), the ionic radius gradually decreases with increasing atomic number because of the influence of the 4f electrons, which show poor shielding of nuclear charge. Rare-earth metal ions generally show strong Lewis acidity and oxophilicity. Rare-earth metal alkyl and hydride species are highly reactive, showing both nucleophilicity and basicity. The combination of these features, such as the strong nucleophilicity and moderate basicity of the alkyl and hydride species and the high stability, strong Lewis acidity, and unsaturated C-C bond affinity of the 3+ metal ions, can make rare-earth metals unique candidates for the formation of excellent single

Technological pretreatment of the synchysite non-oxidized ore

NASA Astrophysics Data System (ADS)

Munkhtsetseg, B.; Burmaa, G.

2013-06-01

Mongolia has rich deposits of rare, precious, and poly-metallic ores. Nowadays, it is important to research separation of rare earth elements oxides concentrates from the ores, analyze their unique physical chemical characteristics, and purified it. Our investigation on raw materials focuses on rare earth non-oxidized ores. Main mineral in this rock sample is Synchysite (LnCa(CO3)2F. We did technological and thermal pretreatment: direct sulphurization (H2SO4), sulphurization with subsequent roasting (800°C+H2SO4), sulphurization prior to roasting (H2SO4+650°C). Sulphurization method based on dissolution of rare earth mineral into sulfuric acid (93%) according to the reaction. The amount of rare earth element oxides is almost 10 times greater (29.16%) after direct sulphurization process, almost 8 times greater (21.14%) after sulphurization with subsequent roasting, and almost 20 times greater (44.62%) after sulphurization prior to roasting process. After those technological pretreatment raw material's micro elements Thorium and Uranium contents are reduced as follows: H2SO4>800°C+H2SO4>H2SO4+650°C. These results show that cerium group rare earth elements have very good solubility in water at +2°C temperature and decreasing micro elements content uranium and thorium good pretreatment condition is prior to roasting (H2SO4+650°C) of synchysite non-oxidized ore.

Effect of nitrogen addition on the structural, electrical, and optical properties of In-Sn-Zn oxide thin films

NASA Astrophysics Data System (ADS)

Jia, Junjun; Torigoshi, Yoshifumi; Suko, Ayaka; Nakamura, Shin-ichi; Kawashima, Emi; Utsuno, Futoshi; Shigesato, Yuzo

2017-02-01

Indium-tin-zinc oxide (ITZO) films were deposited at various nitrogen flow ratios using magnetron sputtering. At a nitrogen flow ratio of 40%, the structure of ITZO film changed from amorphous, with a short-range-ordered In2O3 phase, to a c-axis oriented InN polycrystalline phase, where InN starts to nucleate from an amorphous In2O3 matrix. Whereas, nitrogen addition had no obvious effect on the structure of indium-gallium-zinc oxide (IGZO) films even at a nitrogen flow ratio of 100%. Nitrogen addition also suppressed the formation of oxygen-related vacancies in ITZO films when the nitrogen flow ratio was less than 20%, and higher nitrogen addition led to an increase in carrier density. Moreover, a red-shift in the optical band edge was observed as the nitrogen flow ratio increased, which could be attributed to the generation of InN crystallites. We anticipate that the present findings demonstrating nitrogen-addition induced structural changes can help to understand the environment-dependent instability in amorphous IGZO or ITZO based thin-film transistors (TFTs).

Rare Earth Oxide Fluoride Nanoparticles And Hydrothermal Method For Forming Nanoparticles

DOEpatents

Fulton, John L.; Hoffmann, Markus M.

2003-12-23

A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

Rare earth oxide fluoride nanoparticles and hydrothermal method for forming nanoparticles

DOEpatents

Fulton, John L [Richland, WA; Hoffmann, Markus M [Richland, WA

2001-11-13

A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

The effect of oxidant addition on ferrous iron removal from multi-element acidic sulphate solutions

NASA Astrophysics Data System (ADS)

Mbedzi, Ndishavhelafhi; Ibana, Don; Dyer, Laurence; Browner, Richard

2017-01-01

This study was an investigation on the hydrolytic precipitation of iron from simulated pregnant leach solution (PLS) of nickel laterite atmospheric leaching. The effect of equilibrium pH, temperature and the addition of oxidant on total iron (ferrous (Fe (II)) and ferric (Fe (III)), aluminium and chromium removal was investigated together with the associated nickel and cobalt losses to the precipitate. Systematic variations of the experimental variables revealed ≥99% of the ferric iron can be removed from solution at conditions similar to those used in standard partial neutralisation in zinc and nickel production, pH of 2.5 and temperature less than 100 °C with minimal losses (<0.5%) of both nickel and cobalt. Temperature variation from 55 to 90 °C had no significant effect on the magnitude of Fe (III) precipitation but led to a significant increase in aluminium removal from 67% to 95% and improved the filterability of the precipitates. There was no ferrous iron precipitation even at a pH of 3.75 in the absence of an oxidant with its removal (98%) achieved by oxidative precipitation with oxygen gas at pH 3.5. Unlike Fe (III) precipitation, the operating temperature significantly affects oxidative precipitation of Fe (II). Hence, in practical application, the hydrolytic precipitation and oxidation to remove iron must be operated at 85 °C to ensure both ferrous and ferric iron are precipitated.

Effects of CH3OH Addition on Plasma Electrolytic Oxidation of AZ31 Magnesium Alloys

NASA Astrophysics Data System (ADS)

He, Yongyi; Chen, Li; Yan, Zongcheng; Zhang, Yalei

2015-09-01

Plasma electrolytic oxidation (PEO) films on AZ31 magnesium alloys were prepared in alkaline silicate electrolytes (base electrolyte) with the addition of different volume concentrations of CH3OH, which was used to adjust the thickness of the vapor sheath. The compositions, morphologies, and thicknesses of ceramic layers formed with different CH3OH concentrations were determined via X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), and scanning electron microscopy (SEM). Corrosion behavior of the oxide films was evaluated in 3.5 wt.% NaCl solution using potentiodynamic polarization tests. PEO coatings mainly comprised Mg, MgO, and Mg2SiO4. The addition of CH3OH in base electrolytes affected the thickness, pores diameter, and Mg2SiO4 content in the films. The films formed in the electrolyte containing 12% CH3OH exhibited the highest thickness. The coatings formed in the electrolyte containing different concentrations of CH3OH exhibited similar corrosion resistance. The energy consumption of PEO markedly decreased upon the addition of CH3OH to the electrolytes. The result is helpful for energy saving in the PEO process. supported by National Natural Science Foundation of China (No. 21376088), the Project of Production, Education and Research, Guangdong Province and Ministry of Education (Nos. 2012B09100063, 2012A090300015), and Guangzhou Science and Technology Plan Projects of China (No. 2014Y2-00042)

Properties enhancement of cassava starch based bioplastics with addition of graphene oxide

NASA Astrophysics Data System (ADS)

Amri, A.; Ekawati, L.; Herman, S.; Yenti, S. R.; Zultiniar; Aziz, Y.; Utami, S. P.; Bahruddin

2018-04-01

The properties of cassava starch based bioplastic have been successfully enhanced by additioning of graphene oxide (GO) filler. The composite was synthesized via starch intercalation method using glycerol plasticizer with variation of 5 – 15 % v/v GO filler and mixing time of 30 and 60 minutes. The effects of GO content and the mixing time to the mechanical, water uptake and biodegradation were studied. The synthesis of GO and its integration in the bioplastic composite were also elucidated. The increasing of the GO content and mixing time improved the mechanical properties of composite mainly due to of good homogeneity among the constituents in the composite as indicated by scanning electron microscopy (SEM) and Fourier Transfom Infrared (FTIR) spectroscopy. The bioplastic produced using 15% of GO and 60 minutes mixing time had the highest mechanical properties with tensile strenght of 3,92 Mpa, elongation of 13,22% and modulus young of 29,66 MPa. The water uptake and biodegradation increased as the increase of GO content and decreased as the increase of the mixing time. Graphene oxide is the promissing filler for further development of cassava starch based bioplastics.

Biogenic iron oxide transformation by hyperthermophiles: spectral and physiological potentials

NASA Astrophysics Data System (ADS)

Kashyap, S.; Sklute, E.; Dyar, M. D.; Holden, J. F.

2017-12-01

It is likely that any putative life in our Solar System beyond Earth, extinct or extant, is microbial. However, to detect such life, distinct organic or mineral biosignatures need to be established. Microbe-mineral interactions and mineral transformations deserve further examination in this regard. This study focused on hyperthermophilic iron oxide-reducing archaea and addressed the types of iron-oxide minerals that are favored for growth, the kinetics of such reactions, and the mineral transformations that occur depending upon the electron acceptor. Two hyperthermophilic archaea (Pyrodictium delaneyi and Pyrobaculum islandicum) and six laboratory-synthesized nanophase iron oxide minerals (2-line ferrihydrite, lepidocrocite, akaganéite, goethite, hematite and maghemite) were tested for cell growth and Fe(II) production. The mineral end-products were further characterized by examining the spectral signatures associated with these transformations using reflectance, Raman, and Mössbauer spectroscopies and electron diffraction patterns. Additionally, we critically examined how sample preparation techniques influence the end products of these transformations by comparing freeze-dried samples against those still in solution. Results showed that both organisms utilize all six nanophase iron oxides, although with varying success. The best candidates for microbial reduction were ferrihydrite, akaganéite, and lepidocrocite. The mineral transformation products and the extent of reduction varied and showed subtle differences based on organism and the type of iron oxide used. The subtle spectral differences were best characterized using combined spectroscopy techniques. This research provides new insights into microbe-mineral interactions and the discrimination of potential biosignatures in the search for life beyond Earth.

Water and hydrogen are immiscible in Earth's mantle.

PubMed

Bali, Enikő; Audétat, Andreas; Keppler, Hans

2013-03-14

In the deep, chemically reducing parts of Earth's mantle, hydrous fluids contain significant amounts of molecular hydrogen (H2). Thermodynamic models of fluids in Earth's mantle so far have always assumed that molecular hydrogen and water are completely miscible. Here we show experimental evidence that water and hydrogen can coexist as two separate, immiscible phases. Immiscibility between water and hydrogen may be the cause of the formation of enigmatic, ultra-reducing domains in the mantle that contain moissanite (SiC) and other phases indicative of extremely reducing conditions. Moreover, the immiscibility between water and hydrogen may provide a mechanism for the rapid oxidation of Earth's upper mantle immediately following core formation.

Regional framework and geology of iron oxide-apatite-rare earth element and iron oxide-copper-gold deposits of the Mesoproterozoic St. Francois Mountains Terrane, southeast Missouri

USGS Publications Warehouse

Day, Warren C.; Slack, John F.; Ayuso, Robert A.; Seeger, Cheryl M.

2016-01-01

This paper provides an overview on the genesis of Mesoproterozoic igneous rocks and associated iron oxide ± apatite (IOA) ± rare earth element, iron oxide-copper-gold (IOCG), and iron-rich sedimentary deposits in the St. Francois Mountains terrane of southeast Missouri, USA. The St. Francois Mountains terrane lies along the southeastern margin of Laurentia as part of the eastern granite-rhyolite province. The province formed during two major pulses of igneous activity: (1) an older early Mesoproterozoic (ca. 1.50–1.44 Ga) episode of volcanism and granite plutonism, and (2) a younger middle Mesoproterozoic (ca. 1.33–1.30 Ga) episode of bimodal gabbro and granite plutonism. The volcanic rocks are predominantly high-silica rhyolite pyroclastic flows, volcanogenic breccias, and associated volcanogenic sediments with lesser amounts of basaltic to andesitic volcanic and associated subvolcanic intrusive rocks. The iron oxide deposits are all hosted in the early Mesoproterozoic volcanic and volcaniclastic sequences. Previous studies have characterized the St. Francois Mountains terrane as a classic, A-type within-plate granitic terrane. However, our new whole-rock geochemical data indicate that the felsic volcanic rocks are effusive derivatives from multicomponent source types, having compositional similarities to A-type within-plate granites as well as to S- and I-type granites generated in an arc setting. In addition, the volcanic-hosted IOA and IOCG deposits occur within bimodal volcanic sequences, some of which have volcanic arc geochemical affinities, suggesting an extensional tectonic setting during volcanism prior to emplacement of the ore-forming systems.The Missouri iron orebodies are magmatic-related hydrothermal deposits that, when considered in aggregate, display a vertical zonation from high-temperature, magmatic ± hydrothermal IOA deposits emplaced at moderate depths (~1–2 km), to magnetite-dominant IOA veins and IOCG deposits emplaced at shallow

IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR CERIUM OXIDE (STABLE) AND COMPOUNDS

EPA Science Inventory

Cerium is a member of the lanthanoid series of rare earth metals. It is also the most abundant and most reactive of the rare earth metals. Cerium oxidizes at room temperature and forms a variety of salt compounds including oxides, hydroxides, sulfates and chlorides. Cerium is ...

A combined calorimetric and computational study of the energetics of rare earth substituted UO 2 systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark

2015-09-01

The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are investigated employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towardsmore » increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. However, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.« less

Earth Rotation

NASA Technical Reports Server (NTRS)

Dickey, Jean O.

1995-01-01

The study of the Earth's rotation in space (encompassing Universal Time (UT1), length of day, polar motion, and the phenomena of precession and nutation) addresses the complex nature of Earth orientation changes, the mechanisms of excitation of these changes and their geophysical implications in a broad variety of areas. In the absence of internal sources of energy or interactions with astronomical objects, the Earth would move as a rigid body with its various parts (the crust, mantle, inner and outer cores, atmosphere and oceans) rotating together at a constant fixed rate. In reality, the world is considerably more complicated, as is schematically illustrated. The rotation rate of the Earth's crust is not constant, but exhibits complicated fluctuations in speed amounting to several parts in 10(exp 8) [corresponding to a variation of several milliseconds (ms) in the Length Of the Day (LOD) and about one part in 10(exp 6) in the orientation of the rotation axis relative to the solid Earth's axis of figure (polar motion). These changes occur over a broad spectrum of time scales, ranging from hours to centuries and longer, reflecting the fact that they are produced by a wide variety of geophysical and astronomical processes. Geodetic observations of Earth rotation changes thus provide insights into the geophysical processes illustrated, which are often difficult to obtain by other means. In addition, these measurements are required for engineering purposes. Theoretical studies of Earth rotation variations are based on the application of Euler's dynamical equations to the problem of finding the response of slightly deformable solid Earth to variety of surface and internal stresses.

Earth-approaching asteroid streams

NASA Astrophysics Data System (ADS)

Drummond, J. D.

1991-01-01

Three association patterns have been noted among 139 earth-approaching asteroids on the basis of current orbital similarity; these asteroid streams, consisting of two groups of five members and one of four, can be matched to three of the four meteorite-producing fireball streams determined by Halliday et al. (1990). If the asteroid streams are true nonrandom associations, the opportunity arises for studies of an 'exploded' asteroid in the near-earth environment. Near-earth asteroid-search projects are encouraged to search the mean orbit of the present streams in order to discover additional association members.

Effect of additives on the volatility of elements in a DC arc during the atomic emission analysis of nickel(II) oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zolotareva, N.I.; Kuzyakov, Yu.Ya.; Khlystova, A.D.

1986-10-20

The authors have studied the effect of traditional halogenating additives, AgCl, CdF/sub 2/, PTFE and that of an effective additive they have selected, ZnF/sub 2/, on the volatility of impurity elements, viz. tungsten, molybdenum, titanium, and zirconium from nickel (II) oxide, and determined the constants for the average relative volatility of the elements by the method of Kantor and Pungor. The results have been used to lower the limits of detection of the impurities cited in nickel(II) oxide.

The Formation of Haze During the Rise of Oxygen in the Atmosphere of the Early Earth

NASA Astrophysics Data System (ADS)

Horst, S. M.; Jellinek, M.; Pierrehumbert, R.; Tolbert, M. A.

2014-12-01

also provide a wealth of organic material to the surface. Photochemical hazes are abundant in reducing atmospheres, such as the N2/CH4 atmosphere of Titan, but are unlikely to form in oxidizing atmospheres, such as the N2/O2 atmosphere of present day Earth. However, information about haze formation in mildly oxidizing atmospheres is lacking. Understanding haze formation in mildly oxidizing atmospheres is necessary for models that wish to investigate the atmosphere of the Early Earth as O2 first appeared and then increased in abundance. Previous studies of the atmosphere of the Early Earth have focused on haze formation in N2/CO2/CH4 atmospheres. In this work, we experimentally investigate the effect of the addition of O2 on the formation and composition of aerosols. Using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) (see e.g. [1]) we have obtained in situ composition measurements of aerosol particles produced in N2/CO2/CH4/O2 gas mixtures subjected to FUV radiation (deuterium lamp, 115-400 nm) for a range of initial CO2/CH4/O2 mixing ratios. In particular, we studied the effect of O2 ranging from 2 ppm to 2%. The particles were also investigated using a Scanning Mobility Particle Sizer (SMPS), which measures particle size, number density and mass loading. A comparison of the composition of the aerosols will be presented. The effect of variation of O2 mixing ratio on aerosol production, size, and composition will also be discussed. [1] Trainer, M.G., et al. (2012) Astrobiology, 12, 315-326.

Facilitating atmosphere oxidation through mantle convection

NASA Astrophysics Data System (ADS)

Lee, K. K. M.; Gu, T.; Creasy, N.; Li, M.; McCammon, C. A.; Girard, J.

2017-12-01

Earth's mantle connects the surface with the deep interior through convection, and the evolution of its redox state will affect the distribution of siderophile elements, recycling of refractory isotopes, and the oxidation state of the atmosphere through volcanic outgassing. While the rise of oxygen in the atmosphere, i.e., the Great Oxidation Event (GOE) occurred 2.4 billion years ago (Ga), multiple lines of evidence point to oxygen production in the atmosphere well before 2.4 Ga. In contrast to the fluctuations of atmospheric oxygen, vanadium in Archean mantle lithosphere suggests that the mantle redox state has been constant for 3.5 Ga. Indeed, the connection between the redox state of the deep Earth and the atmosphere is enigmatic as is the effect of redox state on mantle dynamics. Here we show a redox-induced density contrast affects mantle convection and may potentially cause the oxidation of the upper mantle. We compressed two synthetic enstatite chondritic samples with identical bulk compositions but formed under different oxygen fugacities (fO2) to lower mantle pressures and temperatures and find Al2O3 forms its own phase separate from the dominant bridgmanite phase in the more reduced composition, in contrast to a more Al-rich, bridgmanite-dominated assemblage for a more oxidized starting composition. As a result, the reduced material is 1-1.5% denser than the oxidized material. Subsequent experiments on other plausible mantle compositions, which differ only in redox state of the starting glass materials, show similar results: distinct mineral assemblages and density contrasts up to 4%. Our geodynamic simulations suggest that such a density contrast causes a rapid ascent and accumulation of oxidized material in the upper mantle, with descent of the denser reduced material to the core-mantle boundary. The resulting heterogeneous redox conditions in Earth's interior may have contributed to the large low-shear velocity provinces in the lower mantle and the

Effects of cerium on the hydrogen absorption-desorption properties of rare earth-Mg-Ni hydrogen-absorbing alloys

NASA Astrophysics Data System (ADS)

Yasuoka, Shigekazu; Ishida, Jun; Kishida, Kyosuke; Inui, Haruyuki

2017-04-01

The influence of Ce addition on the phase constitution, microstructure, hydrogen absorption/desorption properties and battery performances of newly developed rare earth (RE)-Mg-Ni hydrogen-absorbing superlattice alloys for negative electrode materials in Ni-metal hydride (MH) batteries were investigated. The partial substitution of RE (La and Nd) with Ce results in a higher discharge performance and a lower cycle life in the battery. The Ce addition greatly affects the phase constitution, which is mainly characterized by increased formation of the AB2 phase (A = RE or Mg and B = Ni or Al). The existence of the AB2 phase is found to accelerate alloy pulverization and oxidation when the alloys are used as negative electrode materials in Ni-MH model cells. The accelerated pulverization and oxidation are considered to be responsible for the observed higher discharge performance and lower cycle life in the batteries, respectively.

Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation.

PubMed

Nguyen, Andy I; Ziegler, Micah S; Oña-Burgos, Pascual; Sturzbecher-Hohne, Manuel; Kim, Wooyul; Bellone, Donatela E; Tilley, T Don

2015-10-14

Artificial photosynthesis (AP) promises to replace society's dependence on fossil energy resources via conversion of sunlight into sustainable, carbon-neutral fuels. However, large-scale AP implementation remains impeded by a dearth of cheap, efficient catalysts for the oxygen evolution reaction (OER). Cobalt oxide materials can catalyze the OER and are potentially scalable due to the abundance of cobalt in the Earth's crust; unfortunately, the activity of these materials is insufficient for practical AP implementation. Attempts to improve cobalt oxide's activity have been stymied by limited mechanistic understanding that stems from the inherent difficulty of characterizing structure and reactivity at surfaces of heterogeneous materials. While previous studies on cobalt oxide revealed the intermediacy of the unusual Co(IV) oxidation state, much remains unknown, including whether bridging or terminal oxo ligands form O2 and what the relevant oxidation states are. We have addressed these issues by employing a homogeneous model for cobalt oxide, the [Co(III)4] cubane (Co4O4(OAc)4py4, py = pyridine, OAc = acetate), that can be oxidized to the [Co(IV)Co(III)3] state. Upon addition of 1 equiv of sodium hydroxide, the [Co(III)4] cubane is regenerated with stoichiometric formation of O2. Oxygen isotopic labeling experiments demonstrate that the cubane core remains intact during this stoichiometric OER, implying that terminal oxo ligands are responsible for forming O2. The OER is also examined with stopped-flow UV-visible spectroscopy, and its kinetic behavior is modeled, to surprisingly reveal that O2 formation requires disproportionation of the [Co(IV)Co(III)3] state to generate an even higher oxidation state, formally [Co(V)Co(III)3] or [Co(IV)2Co(III)2]. The mechanistic understanding provided by these results should accelerate the development of OER catalysts leading to increasingly efficient AP systems.

Water oxidation: High five iron

NASA Astrophysics Data System (ADS)

Lloret-Fillol, Julio; Costas, Miquel

2016-03-01

The oxidation of water is essential to the sustainable production of fuels using sunlight or electricity, but designing active, stable and earth-abundant catalysts for the reaction is challenging. Now, a complex containing five iron atoms is shown to efficiently oxidize water by mimicking key features of the oxygen-evolving complex in green plants.

Oxidation stability of biodiesel fuels and blends using the Rancimat and PetroOXY methods. Effect of 4-allyl-2,6-dimetoxiphenol and cathecol as biodiesel additives on oxidation stability

NASA Astrophysics Data System (ADS)

Botella, Lucía; Bimbela, Fernando; Martín, Lorena; Arauzo, Jesús; Sanchez, Jose Luis

2014-07-01

In the present work, several fatty acid methyl esters (FAME) have been synthesized from various fatty acid feedstocks: used frying olive oil, pork fat, soybean, rapeseed, sunflower and coconut. The oxidation stabilities of the biodiesel samples and of several blends have been measured simultaneously by both the Rancimat method, accepted by EN14112 standard, and the PetroOXY method, prEN16091 standard, with the aim of finding a correlation between both methodologies. Other biodiesel properties such as composition, cold filter plugging point (CFPP), flash point (FP) and kinematic viscosity have also been analyzed using standard methods in order to further characterize the biodiesel produced. In addition, the effect on the biodiesel properties of using 4-allyl-2,6-dimetoxiphenol and cathecol as additives in biodiesel blends with rapeseed and with soybean has also been analyzed. The use of both antioxidants results in a considerable improvement in the oxidation stability of both types of biodiesel, especially using cathecol. Adding cathecol loads as low as 0.05 % (m/m) in blends with soybean biodiesel and as low as 0.10 % (m/m) in blends with rapeseed biodiesel is sufficient for the oxidation stabilities to comply with the restrictions established by the European EN14214 standard.An empirical linear equation is proposed to correlate the oxidation stability by the two methods, PetroOXY and Rancimat. It has been found that the presence of either cathecol or 4-allyl-2,6-dimetoxiphenol as additives affects the correlation observed.

Thermoelectric Power Generation from Lanthanum Strontium Titanium Oxide at Room Temperature through the Addition of Graphene.

PubMed

Lin, Yue; Norman, Colin; Srivastava, Deepanshu; Azough, Feridoon; Wang, Li; Robbins, Mark; Simpson, Kevin; Freer, Robert; Kinloch, Ian A

2015-07-29

The applications of strontium titanium oxide based thermoelectric materials are currently limited by their high operating temperatures of >700 °C. Herein, we show that the thermal operating window of lanthanum strontium titanium oxide (LSTO) can be reduced to room temperature by the addition of a small amount of graphene. This increase in operating performance will enable future applications such as generators in vehicles and other sectors. The LSTO composites incorporated one percent or less of graphene and were sintered under an argon/hydrogen atmosphere. The resultant materials were reduced and possessed a multiphase structure with nanosized grains. The thermal conductivity of the nanocomposites decreased upon the addition of graphene, whereas the electrical conductivity and power factor both increased significantly. These factors, together with a moderate Seebeck coefficient, meant that a high power factor of ∼2500 μWm(-1)K(-2) was reached at room temperature at a loading of 0.6 wt % graphene. The highest thermoelectric figure of merit (ZT) was achieved when 0.6 wt % graphene was added (ZT = 0.42 at room temperature and 0.36 at 750 °C), with >280% enhancement compared to that of pure LSTO. A preliminary 7-couple device was produced using bismuth strontium cobalt oxide/graphene-LSTO pucks. This device had a Seebeck coefficient of ∼1500 μV/K and an open voltage of 600 mV at a mean temperature of 219 °C.

Variation of Aging Precipitates and Mechanical Strength of Al-Cu-Li Alloys Caused by Small Addition of Rare Earth Elements

NASA Astrophysics Data System (ADS)

Ma, Yun-long; Li, Jin-feng

2017-09-01

The effect of small rare earth (RE) addition of 0.11%Ce, 0.2%Er and 0.082%Sc on aging precipitates and mechanical strength of an Al-(3.3-4.2)Cu-1.2Li-X alloy were investigated. It is found that Cu-rich residual particles containing RE element exist in the solutionized alloy, which leads to a decrease of dissolved Cu concentration in the solutionized matrix. Like RE-free alloy, the main aging precipitate types in RE-containing alloy are T1 (Al2CuLi) and θ' (Al2Cu), but their fraction is decreased. The strength of the corresponding alloys is therefore lowered by the small RE addition. Combined with the analysis of some reported references, it is proposed that the effect of small RE addition on Al-Cu-Li alloy strength is also associated with the Cu and Li concentrations and their ratio.

Effect of the Cerium Oxide (CeO2) on the Structural and Electrochemical Properties of the LaNi5Ce Metal Hydride Anode

NASA Astrophysics Data System (ADS)

Utami Hapsari, Ade; Zulfia, Anne; Raharjo, Jarot; Agustanhakri

2017-07-01

One of negative electrode, AB5-type alloy electrodes, have been extensively studied and applied in rechargeable Ni-MH batteries due to their excellent electrochemical characteristics. Some researchers have found that addition of rare earth oxides (La, Ce, Pr, Er, Tm, Yb) to AB5-type alloy (MH) electrode improves battery performance significantly. Cerium Oxide (CeO2) is a light rare earth oxide is widely obtained from the processing of tailings in mining activities. During this time, there is still little data for research applications of cerium oxide for electrode materials. In this paper, the effects of adding CeO2 on the performance metal hydride electrode were investigated. In order to study the effects of CeO2 on the performance of anode material, 1%, 2%, and 3% of weight ratio CeO2 was mixed to LaNi5 as an negative electrode. The powder mixtures were mechanically milled at a speed of rpm 240 for 2 hours using ball mill. The powder mixtures were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). Electrochemical characteristics were measured using electrochemical impedance spectroscopy (EIS). The powder mixing showed the presence of Ce atom substitution into LaNi5 structures that affect the electrochemical properties of the material. The addition of cerium oxide at LaNi5 increase of the value of impedance. However, the addition of the value of impedance at 1% CeO2 is not significant when compared with the addition of 2% and 3% CeO2 that actually make the electrochemical properties of LaNi5 worst. Although the addition of 1% CeO2 also slightly increases the impedance value of LaNi5, but the addition of 1% CeO2 showed increase the corrosion resistance than without the addition of CeO2 and the addition of 2% and 3% CeO2.

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †.

PubMed

Afzal, Adeel; Dickert, Franz L

2018-04-20

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed.

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †

PubMed Central

2018-01-01

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed. PMID:29677107

Skylab explores the Earth

NASA Technical Reports Server (NTRS)

1977-01-01

Data from visual observations are integrated with results of analyses of approxmately 600 of the nearly 2000 photographs taken of Earth during the 84-day Skylab 4 mission to provide additional information on (1) Earth features and processes; (2) operational procedures and constraints in observing and photographing the planet; and (3) the use of man in real-time analysis of oceanic and atmospheric phenomena.

Microstructural and electrical characteristics of rare earth oxides doped ZnO varistor films

NASA Astrophysics Data System (ADS)

Jiao, Lei; Mei, Yunzhu; Xu, Dong; Zhong, Sujuan; Ma, Jia; Zhang, Lei; Bao, Li

2018-02-01

ZnO-Bi2O3 varistor films doped with two kinds of rare earth element oxides (Lu2O3 and Yb2O3) were prepared by the sol-gel method. The effects of Lu2O3/Yb2O3 doping on the microstructure and electrical characteristics of ZnO-Bi2O3 varistor films were investigated. All samples show a homogenized morphology and an improved nonlinear relationship between the electric field (E) and current density (I). Both Yb2O3 and Lu2O3 doping can decrease the grain size of ZnO-Bi2O3 varistor films and improve the electrical properties, which have a positive effect on the development of ZnO varistor ceramics. Yb2O3 doping significantly increases the dielectric constant at low frequency. 0.2 mol. % Yb2O3 doped ZnO-Bi2O3 varistor films exhibit the highest nonlinear coefficient (2.5) and the lowest leakage current (328 μA) among Lu2O3/Yb2O3 doped ZnO-Bi2O3 varistor films. Similarly, 0.1 mol. % Lu2O3 doping increases the nonlinear coefficient to 1.9 and decrease the leakage current to 462 μA.

Methanol Oxidative Dehydrogenation on Oxide Catalysts: Molecular and Dissociative Routes and Hydrogen Addition Energies as Descriptors of Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deshlahra, Prashant; Iglesia, Enrique

The oxidative dehydrogenation (ODH) of alkanols on oxide catalysts is generally described as involving H-abstraction from alkoxy species formed via O–H dissociation. Kinetic and isotopic data cannot discern between such routes and those involving kinetically-relevant H-abstraction from undissociated alkanols. Here, we combine such experiments with theoretical estimates of activation energies and entropies to show that the latter molecular routes prevail over dissociative routes for methanol reactions on polyoxometalate (POM) clusters at all practical reaction temperatures. The stability of the late transition states that mediate H-abstraction depend predominantly on the stability of the O–H bond formed, making H-addition energies (HAE) accuratemore » and single-valued descriptors of reactivity. Density functional theory-derived activation energies depend linearly on HAE values at each O-atom location on clusters with a range of composition (H3PMo12, H4SiMo12, H3PW12, H4PV1Mo11, and H4PV1W11); both barriers and HAE values reflect the lowest unoccupied molecular orbital energy of metal centers that accept the electron and the protonation energy of O-atoms that accept the proton involved in the H-atom transfer. Bridging O-atoms form O–H bonds that are stronger than those of terminal atoms and therefore exhibit more negative HAE values and higher ODH reactivity on all POM clusters. For each cluster composition, ODH turnover rates reflect the reactivity-averaged HAE of all accessible O-atoms, which can be evaluated for each cluster composition to provide a rigorous and accurate predictor of ODH reactivity for catalysts with known structure. These relations together with oxidation reactivity measurements can then be used to estimate HAE values and to infer plausible structures for catalysts with uncertain active site structures.« less

Accessibility of near-Earth asteroids, 1990

NASA Technical Reports Server (NTRS)

Hulkower, Neal D.; Child, Jack B.

1991-01-01

Previous research which analyzed the accessibility of all known near-Earth asteroids is updated. Since then, many new near-Earth asteroids have been discovered, and 1928 DB, the most accessible asteroid at that time, has been recovered. Many of these recently discovered near-Earth asteroids have promising orbital characteristics. In addition to accessibility (as defined by minimum global delta v), ideal rendezvous opportunities are identified.

Tantalum Addition to Zirconium Diboride for Improved Oxidation Resistance

NASA Technical Reports Server (NTRS)

Levine, Stanley R.; Opila, Eliizabeth J.

2003-01-01

Ultrahigh temperature ceramics have performed unreliably due to material flaws and attachment design. These deficiencies are brought to the fore by the low fracture toughness and thermal shock resistance of UHTCs. If these deficiencies are overcome, we are still faced with poor oxidation resistance as a limitation on UHTC applicability to reusable launch vehicles. We have been addressing the deficiencies of UHTCs with our focus on composite constructions and functional grading to address the mechanical issues, and on composition modification to address the oxidation issue. The approaches and progress toward the latter are reported.

Generic process for preparing a crystalline oxide upon a group IV semiconductor substrate

DOEpatents

McKee, Rodney A.; Walker, Frederick J.; Chisholm, Matthew F.

2000-01-01

A process for growing a crystalline oxide epitaxially upon the surface of a Group IV semiconductor, as well as a structure constructed by the process, is described. The semiconductor can be germanium or silicon, and the crystalline oxide can generally be represented by the formula (AO).sub.n (A'BO.sub.3).sub.m in which "n" and "m" are non-negative integer repeats of planes of the alkaline earth oxides or the alkaline earth-containing perovskite oxides. With atomic level control of interfacial thermodynamics in a multicomponent semiconductor/oxide system, a highly perfect interface between a semiconductor and a crystalline oxide can be obtained.

Oxidation of ZrB2-and HfB2-Based Ultra-High Temperature Ceramics: Effects of Ta Additions

NASA Technical Reports Server (NTRS)

Opila, Elizabeth; Levine, Stanley; Lorinez, Jonathan

2003-01-01

Several compositions of ZrB2- and HfB2-based Ultra-High Temperature Ceramics (UHTC) were oxidized in stagnant air at 1627 C in ten minute cycles for times up to 100 minutes. These compositions include: ZrB2 - 20v% SiC, HfB2 - 20v% SiC, ZrB2 - 20v% SiC - 20v% TaSi2, ZrB2 - 33v% SiC, HfB2 - 20v% SiC - 20v% TaSi2, and ZrB2 - 20v% SiC - 20v% TaC. The weight change due to oxidation was recorded. The ZrB2 - 20v% SiC - 20v% TaSi2 composition was also oxidized in stagnant air at 1927 C and in an arc jet atmosphere. Samples were analyzed after oxidation by x-ray diffraction, field emission scanning electron microscopy, and energy dispersive spectroscopy to determine the reaction products and to observe the microstructure. The ZrB2 - 20v% SiC - 20v% TaSi2 showed the lowest oxidation rate at 1627 C, but performed poorly under the more extreme tests due to liquid phase formation. Effects of Ta-additions on the oxidation of the diboride-based UHTC are discussed.

Nitric oxide and S-nitrosoglutathione function additively during plant immunity.

PubMed

Yun, Byung-Wook; Skelly, Michael J; Yin, Minghui; Yu, Manda; Mun, Bong-Gyu; Lee, Sang-Uk; Hussain, Adil; Spoel, Steven H; Loake, Gary J

2016-07-01

Nitric oxide (NO) is emerging as a key regulator of diverse plant cellular processes. A major route for the transfer of NO bioactivity is S-nitrosylation, the addition of an NO moiety to a protein cysteine thiol forming an S-nitrosothiol (SNO). Total cellular levels of protein S-nitrosylation are controlled predominantly by S-nitrosoglutathione reductase 1 (GSNOR1) which turns over the natural NO donor, S-nitrosoglutathione (GSNO). In the absence of GSNOR1 function, GSNO accumulates, leading to dysregulation of total cellular S-nitrosylation. Here we show that endogenous NO accumulation in Arabidopsis, resulting from loss-of-function mutations in NO Overexpression 1 (NOX1), led to disabled Resistance (R) gene-mediated protection, basal resistance and defence against nonadapted pathogens. In nox1 plants both salicylic acid (SA) synthesis and signalling were suppressed, reducing SA-dependent defence gene expression. Significantly, expression of a GSNOR1 transgene complemented the SNO-dependent phenotypes of paraquat resistant 2-1 (par2-1) plants but not the NO-related characters of the nox1-1 line. Furthermore, atgsnor1-3 nox1-1 double mutants supported greater bacterial titres than either of the corresponding single mutants. Our findings imply that GSNO and NO, two pivotal redox signalling molecules, exhibit additive functions and, by extension, may have distinct or overlapping molecular targets during both immunity and development. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Effects of pyrolysis temperature, time and leaf litter and powder coal ash addition on sludge-derived adsorbents for nitrogen oxide.

PubMed

Ren, Xiaoli; Liang, Baohong; Liu, Min; Xu, Xiaoyuan; Cui, Meihua

2012-12-01

The objective of this research was to seek a cost effective solution to prepare adsorbents for nitrogen oxide from surplus sludge. Leaf litter and powder coal ash were used as cheap and easily available additives. An adsorbent for nitrogen oxide was prepared by pyrolysis of dried sludge mixed with zinc chloride. Under optimum pyrolysis conditions of 375°C for 90 min and a zinc chloride content of 30%, the surface area of the adsorbent with leaf litter was 514.41 m(2)/g, the surface area of the adsorbent with powder coal ash was 432.34 m(2)/g, respectively, corresponding to an increase of 90.70% and 60.27% when compared to the adsorbent without the additives. The saturated adsorption quantity of the adsorbent with leaf litter reached 271 mg/g at 20°C. The results indicated that the sludge-derived adsorbent was quite promising for nitrogen oxide removal. Copyright © 2012 Elsevier Ltd. All rights reserved.

Mixed alkali effect on the spectroscopic properties of alkali-alkaline earth oxide borate glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Srinivas, G., E-mail: srinu123g@gmail.com; Ramesh, B.; Shareefuddin, Md.

2016-05-06

The mixed alkali and alkaline earth oxide borate glass with the composition xK{sub 2}O - (25-x) Li{sub 2}O-12.5BaO-12.5MgO-50B{sub 2}O{sub 3} (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α{sub 0}2-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α{sub 0}2-), and (Λ) increases with increasing of K{sub 2}O content and electronicmore » polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K{sub 2}O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).« less

Forming-free colossal resistive switching effect in rare-earth-oxide Gd2O3 films for memristor applications

NASA Astrophysics Data System (ADS)

Cao, Xun; Li, Xiaomin; Gao, Xiangdong; Yu, Weidong; Liu, Xinjun; Zhang, Yiwen; Chen, Lidong; Cheng, Xinhong

2009-10-01

The reproducible forming-free resistive switching (RS) behavior in rare-earth-oxide Gd2O3 polycrystalline thin film was demonstrated. The characteristic of this forming-free RS was similar to that of other forming-necessary binary RS materials except that its initial resistance starts from not the high resistance state (HRS) but the low resistance state (LRS). An ultrahigh resistance switching ratio from HRS to LRS of about six to seven orders of magnitude was achieved at a bias voltage of 0.6 V. Mechanism analysis indicated that the existence of metallic Gd in the Gd2O3 films plays an important role in the forming-free RS performance. Our work provides a novel material with interesting RS behavior, which is beneficial to deepen our understanding of the origin of RS phenomenon.

CLOUDS IN SUPER-EARTH ATMOSPHERES: CHEMICAL EQUILIBRIUM CALCULATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mbarek, Rostom; Kempton, Eliza M.-R., E-mail: mbarekro@grinnell.edu, E-mail: kemptone@grinnell.edu

Recent studies have unequivocally proven the existence of clouds in super-Earth atmospheres. Here we provide a theoretical context for the formation of super-Earth clouds by determining which condensates are likely to form under the assumption of chemical equilibrium. We study super-Earth atmospheres of diverse bulk composition, which are assumed to form by outgassing from a solid core of chondritic material, following Schaefer and Fegley. The super-Earth atmospheres that we study arise from planetary cores made up of individual types of chondritic meteorites. They range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solarmore » and super-solar, thereby spanning a range of atmospheric composition that is appropriate for low-mass exoplanets. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of formation for over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350–3000 K. Clouds should form along the temperature–pressure boundaries where the condensed species appear in our calculation. We find that the composition of condensate clouds depends strongly on both the H:O and C:O ratios. For the super-Earth archetype GJ 1214b, KCl and ZnS are the primary cloud-forming condensates at solar composition, in agreement with previous work. However, for oxidizing atmospheres, K{sub 2}SO{sub 4} and ZnO condensates are favored instead, and for carbon-rich atmospheres with super-solar C:O ratios, graphite clouds appear. For even hotter planets, clouds form from a wide variety of rock-forming and metallic species.« less

Clouds in Super-Earth Atmospheres: Chemical Equilibrium Calculations

NASA Astrophysics Data System (ADS)

Mbarek, Rostom; Kempton, Eliza M.-R.

2016-08-01

Recent studies have unequivocally proven the existence of clouds in super-Earth atmospheres. Here we provide a theoretical context for the formation of super-Earth clouds by determining which condensates are likely to form under the assumption of chemical equilibrium. We study super-Earth atmospheres of diverse bulk composition, which are assumed to form by outgassing from a solid core of chondritic material, following Schaefer & Fegley. The super-Earth atmospheres that we study arise from planetary cores made up of individual types of chondritic meteorites. They range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solar and super-solar, thereby spanning a range of atmospheric composition that is appropriate for low-mass exoplanets. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of formation for over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350-3000 K. Clouds should form along the temperature-pressure boundaries where the condensed species appear in our calculation. We find that the composition of condensate clouds depends strongly on both the H:O and C:O ratios. For the super-Earth archetype GJ 1214b, KCl and ZnS are the primary cloud-forming condensates at solar composition, in agreement with previous work. However, for oxidizing atmospheres, K2SO4 and ZnO condensates are favored instead, and for carbon-rich atmospheres with super-solar C:O ratios, graphite clouds appear. For even hotter planets, clouds form from a wide variety of rock-forming and metallic species.

Effects of oxidization and deoxidization on charge-propagation dynamics in rare-earth-doped titanium dioxide with room-temperature luminescence

NASA Astrophysics Data System (ADS)

Ishii, Masashi; Towlson, Brian; Poolton, Nigel; Harako, Susumu; Zhao, Xinwei; Komuro, Shuji; Hamilton, Bruce

2012-03-01

Anatase titanium dioxide (A-TiO2) with a wide band-gap energy of 3.2 eV can be used as a host semiconductor of rare-earth dopants for optical devices. However, the chemical activity of A-TiO2 strongly affects the luminescence properties of the devices. In this study, we analyzed oxidized and deoxidized samarium (Sm)-doped A-TiO2 (TiO2:Sm) by impedance spectroscopy and microscopic photoluminescence. Charge propagation analyses using dielectric relaxation (DR) revealed that different kinds of charge-trapping centers were formed by the oxidization and deoxidization. For oxidization, Sm-oxygen complexes incorporated in the A-TiO2 formed a trapping level that contributed to Sm excitation, while defective complexes at the A-TiO2 boundary formed other levels that dissipated the charges. For deoxidization using thermal treatment in a hydrogen (H) atmosphere, the number of profitable trapping centers in A-TiO2 was reduced but the remainder maintained the property of Sm excitation. It was also found that H adsorption on the A-TiO2 boundary delocalized the electrons. Photoexcited dielectric relaxation (PEDR) studies confirmed the charge recombination at the profitable traps, and the peak height of the spectra corresponded to the luminescence intensity. Microscopic photoluminescence studies provided results consistent with DR and PEDR measurements and also revealed another quenching factor, i.e., Ti2O3 microcrystal formation on the TiO2:Sm surface.

The Earth Tides.

ERIC Educational Resources Information Center

Levine, Judah

1982-01-01

In addition to oceans, the earth is subjected to tidal stresses and undergoes tidal deformations. Discusses origin of tides, tidal stresses, and methods of determining tidal deformations (including gravity, tilt, and strain meters). (JN)

Structure-property-composition relationships in doped zinc oxides: enhanced photocatalytic activity with rare earth dopants.

PubMed

Goodall, Josephine B M; Illsley, Derek; Lines, Robert; Makwana, Neel M; Darr, Jawwad A

2015-02-09

In this paper, we demonstrate the use of continuous hydrothermal flow synthesis (CHFS) technology to rapidly produce a library of 56 crystalline (doped) zinc oxide nanopowders and two undoped samples, each with different particle properties. Each sample was produced in series from the mixing of an aqueous stream of basic zinc nitrate (and dopant ion or modifier) solution with a flow of superheated water (at 450 °C and 24.1 MPa), whereupon a crystalline nanoparticle slurry was rapidly formed. Each composition was collected in series, cleaned, freeze-dried, and then characterized using analytical methods, including powder X-ray diffraction, transmission electron microscopy, Brunauer-Emmett-Teller surface area measurement, X-ray photoelectron spectroscopy, and UV-vis spectrophotometry. Photocatalytic activity of the samples toward the decolorization of methylene blue dye was assessed, and the results revealed that transition metal dopants tended to reduce the photoactivity while rare earth ions, in general, increased the photocatalytic activity. In general, low dopant concentrations were more beneficial to having greater photodecolorization in all cases.

Addressing Rare-Earth Element Criticality: An Example from the Aviation Industry

NASA Astrophysics Data System (ADS)

Ku, Anthony Y.; Dosch, Christopher; Grossman, Theodore R.; Herzog, Joseph L.; Maricocchi, Antonio F.; Polli, Drew; Lipkin, Don M.

2014-11-01

Rare-earth (RE) elements are enablers for a wide range of technologies, including high-strength permanent magnets, energy-efficient lighting, high-temperature thermal barrier coatings, and catalysts. While direct material substitution is difficult in many of these applications because of the specific electronic, optical, or electrochemical properties imparted by the individual rare-earth elements, we describe an example from the aviation industry where supply chain optimization may be an option. Ceramic matrix composite engine components require environmental barrier coatings (EBCs) to protect them from extreme temperatures and adverse reactions with water vapor in the hot gas path. EBC systems based on rare-earth silicates offer a unique combination of environmental resistance, thermal expansion matching, thermal conductivity, and thermal stability across the service temperature window. Several pure rare-earth silicates and solid solutions have been demonstrated in EBC applications. However, all rely on heavy rare-earth elements (HREEs) for phase stability. This article considers the possibility of using separation tailings containing a mixture of HREEs as a source material in lieu of using the high-purity HREE oxides. This option arises because the desired properties of RE-silicate EBCs derive from the average cation size rather than the electronic properties of the individual rare-earth cations. Because separation tailings have not incurred the costs associated with the final stages of separation, they offer an economical alternative to high-purity oxides for this emerging application.

Stabilized tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Watkins, Anthony Neal (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Jordan, Jeffrey D. (Inventor); Schryer, Jacqueline L. (Inventor)

2008-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Formal oxidative addition of a C-H bond by a 16e iridium(i) complex involves metal-ligand cooperation.

PubMed

Kumar, Amit; Feller, Moran; Ben-David, Yehoshoa; Diskin-Posner, Yael; Milstein, David

2018-05-10

The first example of oxidative addition of a C-H bond to a square planar d8-Iridium complex, without any external additive, such as an acid, is described. Our mechanistic investigations show that metal-ligand cooperation through aromatization-dearomatization of the lutidine backbone is involved in this process, and that the actual C-H activation step occurs through an Ir(iii) intermediate.

Earth Viewing Applications Laboratory (EVAL). Instrument catalog

NASA Technical Reports Server (NTRS)

1976-01-01

There were 87 instruments described that are used in earth observation, with an additional 51 instruments containing references to programs and their major functions. These instruments were selected from such sources as: (1) earth observation flight program, (2) operational satellite improvement programs, (3) advanced application flight experiment program, (4) shuttle experiment definition program, and (5) earth observation aircraft program.

Bis(tri-n-hexylsilyl oxide) silicon phthalocyanine: a unique additive in ternary bulk heterojunction organic photovoltaic devices.

PubMed

Lessard, Benoît H; Dang, Jeremy D; Grant, Trevor M; Gao, Dong; Seferos, Dwight S; Bender, Timothy P

2014-09-10

Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS)2-SiPc) as an additive in a P3HT:PC61BM cascade ternary bulk heterojunction organic photovoltaic (BHJ OPV) device results in an increase in the short circuit current (J(SC)) and efficiency (η(eff)) of up to 25% and 20%, respectively. The previous studies have attributed the increase in performance to the presence of (3HS)2-SiPc at the BHJ interface. In this study, we explored the molecular characteristics of (3HS)2-SiPc which makes it so effective in increasing the OPV device J(SC) and η(eff. Initially, we synthesized phthalocyanine-based additives using different core elements such as germanium and boron instead of silicon, each having similar frontier orbital energies compared to (3HS)2-SiPc and tested their effect on BHJ OPV device performance. We observed that addition of bis(tri-n-hexylsilyl oxide) germanium phthalocyanine ((3HS)2-GePc) or tri-n-hexylsilyl oxide boron subphthalocyanine (3HS-BsubPc) resulted in a nonstatistically significant increase in JSC and η(eff). Secondly, we kept the silicon phthalocyanine core and substituted the tri-n-hexylsilyl solubilizing groups with pentadecyl phenoxy groups and tested the resulting dye in a BHJ OPV. While an increase in JSC and η(eff) was observed at low (PDP)2-SiPc loadings, the increase was not as significant as (3HS)2-SiPc; therefore, (3HS)2-SiPc is a unique additive. During our study, we observed that (3HS)2-SiPc had an extraordinary tendency to crystallize compared to the other compounds in this study and our general experience. On the basis of this observation, we have offered a hypothesis that when (3HS)2-SiPc migrates to the P3HT:PC61BM interface the reason for its unique performance is not solely due to its frontier orbital energies but also might be due to a high driving force for crystallization.

Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.

NASA Astrophysics Data System (ADS)

Johannesson, Kevin H.; Zhou, Xiaoping

1999-01-01

-Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.

The Formation of Haze During the Rise of Oxygen in the Atmosphere of the Early Earth

NASA Astrophysics Data System (ADS)

Horst, S. M.; Jellinek, M.; Pierrehumbert, R.; Tolbert, M. A.

2013-12-01

Atmospheric aerosols play an important role in determining the radiation budget of an atmosphere and can also provide a wealth of organic material to the surface. Photochemical hazes are abundant in reducing atmospheres, such as the N2/CH4 atmosphere of Titan, but are unlikely to form in oxidizing atmospheres, such as the N2/O2 atmosphere of present day Earth. However, information about haze formation in mildly oxidizing atmospheres is lacking. Understanding haze formation in mildly oxidizing atmospheres is necessary for models that wish to investigate the atmosphere of the Early Earth as O2 first appeared and then increased in abundance. Previous studies of the atmosphere of the Early Earth have focused on haze formation in N2/CO2/CH4 atmospheres. In this work, we experimentally investigate the effect of the addition of O2 on the formation and composition of aerosols. Using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) (see e.g. [1]) we have obtained in situ composition measurements of aerosol particles produced in N2/CO2/CH4/O2 gas mixtures subjected to FUV radiation (deuterium lamp, 115-400 nm) for a range of initial CO2/CH4/O2 mixing ratios. In particular, we studied the effect of O2 ranging from 2 ppm to 2%. The particles were also investigated using a Scanning Mobility Particle Sizer (SMPS), which measures particle size, number density and mass loading. A comparison of the composition of the aerosols will be presented. The effect of variation of O2 mixing ratio on aerosol production, size, and composition will also be discussed. [1] Trainer, M.G., et al. (2012) Astrobiology, 12, 315-326.

Molybdenum isotopes reveal oxidation of Earth's continental crust during the 2.4 Ga Great Oxidation Event

NASA Astrophysics Data System (ADS)

Greaney, A. T.; Rudnick, R. L.; Romaniello, S. J.; Johnson, A.; Gaschnig, R. M.; Anbar, A. D.

2017-12-01

Concentrations of redox sensitive metals in ocean sediments have been used to infer the onset of oxidative weathering at the time of the GOE, however little is known about the complimentary continental reservoir from which these metals were sourced. Gaschnig et al. (2014) demonstrated that glacial diamictites, which are mixtures of weathered regolith and unweathered upper continental crust (UCC), are systematically depleted in Mo following the GOE. This depletion is attributed to the onset of oxidative weathering, which removed soluble oxidized Mo6+ from the UCC. To determine if Mo isotope fractionation supports this hypothesis, we measured Mo isotopes in twenty-four composites of glacial diamictites spanning depositional ages of 2.9 Ga to 300 Ma. The diamictites fall into three age groups: pre-GOE (2.43 - 2.90 Ga), syn-GOE (2.20 - 2.39 Ga), and syn/post-NOE (0.33 - 0.75 Ga). Pre-GOE composites have an average δ98MoNIST of +0.03‰, syn-GOE composites average -0.29‰, and syn/post-NOE composites average -0.45‰; these groups are statistically different at p=0.01. These data imply that the onset of oxidative weathering, which removed Mo from the UCC, also caused isotopic fractionation of Mo. We speculate that this fractionation is due to isotopically light Mo being adsorbed onto Fe-Mn oxides that formed in soils under an oxic atmosphere, leaving heavy Mo to be transported in solution to rivers. Rayleigh fractionation and mixing models support the incorporation of Fe-Mn oxides into soils that were sampled by the diamictites after the GOE. As these phases are not stable under an anoxic atmosphere, the pre-GOE diamictites are isotopically indistinguishable from igneous UCC (0.0 to +0.15‰, Liang et al., 2017; Willbold et al., 2017). The 2.39 Ga Duitschland diamictite is exceptionally light (-0.80‰), suggesting oxidative weathering was extreme in some locations at the onset of the GOE. We conclude that Mo isotopes have been fractionated upon removal from the UCC

Application of Mössbauer Spectroscopy in Earth Sciences

NASA Astrophysics Data System (ADS)

Vandenberghe, Robert E.; De Grave, Eddy

Iron being the fourth most abundant element in the earth crust, 57Fe Mössbauer spectroscopy has become a suitable additional technique for the characterization of all kind of soil materials and minerals. However, for that purpose a good knowledge of the spectral behavior of the various minerals is indispensable. In this chapter a review of the most important soil materials and rock-forming minerals is presented. It starts with a description of the Mössbauer spectroscopic features of the iron oxides and hydroxides, which are essentially present in soils and sediments. Further, the Mössbauer spectra from sulfides, sulfates and carbonates are briefly considered. Finally, the Mössbauer features of the typical and most common silicate and phosphate minerals are reported. The chapter ends with some typical examples, illustrating the use and power of Mössbauer spectroscopy in the characterization of minerals.

Our Mission to Planet Earth: A guide to teaching Earth system science

NASA Technical Reports Server (NTRS)

1994-01-01

Volcanic eruptions, hurricanes, floods, and El Nino are naturally occurring events over which humans have no control. But can human activities cause additional environmental change? Can scientists predict the global impacts of increased levels of pollutants in the atmosphere? Will the planet warm because increased levels of greenhouse gases, produced by the burning of fossil fuels, trap heat and prevent it from being radiated back into space? Will the polar ice cap melt, causing massive coastal flooding? Have humans initiated wholesale climatic change? These are difficult questions, with grave implications. Predicting global change and understanding the relationships among earth's components have increased in priority for the nation. The National Aeronautics and Space Administration (NASA), along with many other government agencies, has initiated long-term studies of earth's atmosphere, oceans, and land masses using observations from satellite, balloon, and aircraft-borne instruments. NASA calls its research program Mission to Planet Earth. Because NASA can place scientific instruments far above earth's surface, the program allows scientists to explore earth's components and their interactions on a global scale.

Impact of green tea extract addition on oxidative changes in the lipid fraction of pastry products.

PubMed

Żbikowska, Anna; Kowalska, Małgorzata; Rutkowska, Jarosława; Kozłowska, Mariola; Onacik-Gür, Sylwia

2017-01-01

Alongside flour, fat is the key ingredient of sponge cakes, including those with long shelf lives. It is an unstable food component, whose quality and nutritional safety depend on the composition and pres- ence of oxidation products. Consumption of fat oxidation products adversely affects the human body and contributes to the incidence of a number of medical conditions. Qualitative changes in fats extracted from thermostat sponge cakes with and without antioxidant additions were determined in this study. In the study, two types of antioxidant were used: natural - green tea extract in three doses (0.02%; 0.2% and 1.0%) and synthetic BHA (0.02%) and 100%, solid bakery shortening. Sponge-cakes were thermostatted at temperatures 63°C after twenty-eight days. In this study, the quality of the lipid fraction was analyzed. The amount of primary (PV) and secondary (AnV) oxidation products was determined, and   a Rancimat test was performed. Adding antioxidants to fats varied in the degree to which oxidation processes of lipids fractions were inhibited. The peroxide value after twenty-eight days of thermostatting ranged from 3.57 meq O/kg (BHA) and 11.14 O meq/kg (extract content - 1%) to 62.85 meq O/kg (control sample). In turn, the value of AnV after the storage period ranged from 4.84 (BHA) and 6.71 (extract content - 1%) to 16.83 (control sample). The best protective effects in the process of oxidation was achieved by BHA. The longest in- duction time and the lowest peroxide value and anisidine value were obtained for this antioxidant. It was achieved after twenty-eight days of fat thermostatting. Nonetheless, the results demonstrated it is possible to use the commercially available green tea extract to slow the adverse process of fat oxidation in sponge cake products.

Oxides for sustainable photovoltaics with earth-abundant materials

NASA Astrophysics Data System (ADS)

Wagner, Alexander; Stahl, Mathieu; Ehrhardt, Nikolai; Fahl, Andreas; Ledig, Johannes; Waag, Andreas; Bakin, Andrey

2014-03-01

Energy conversion technologies are aiming to extremely high power capacities per year. Nontoxicity and abundance of the materials are the key requirements to a sustainable photovoltaic technology. Oxides are among the key materials to reach these goals. We investigate the influence of thin buffer layers on the performance of an ZnO:Al/buffer/Cu2O solar cells. Introduction of a thin ZnO or Al2O3 buffer layer, grown by thermal ALD, between ZnO:Al and Cu2O resulted in 45% increase of the solar cell efficiency. VPE growth of Cu2O employing elemental copper and pure oxygen as precursor materials is presented. The growth is performed on MgO substrates with the (001) orientation. On- and off- oriented substrates have been employed and the growth results are compared. XRD investigations show the growth of the (110) oriented Cu2O for all temperatures, whereas at a high substrate temperature additional (001) Cu2O growth occurs. An increase of the oxygen partial pressure leads to a more pronounced 2D growth mode, whereby pores between the islands still remain. The implementation of off-axis substrates with 3.5° and 5° does not lead to an improvement of the layer quality. The (110) orientation remains predominant, the grain size decreases and the FWHM of the (220) peak increases. From the AFM images it is concluded, that the (110) surface grows with a tilt angle to the substrate surface.

Air electrode composition for solid oxide fuel cell

DOEpatents

Kuo, Lewis; Ruka, Roswell J.; Singhal, Subhash C.

1999-01-01

An air electrode composition for a solid oxide fuel cell is disclosed. The air electrode material is based on lanthanum manganite having a perovskite-like crystal structure ABO.sub.3. The A-site of the air electrode composition comprises a mixed lanthanide in combination with rare earth and alkaline earth dopants. The B-site of the composition comprises Mn in combination with dopants such as Mg, Al, Cr and Ni. The mixed lanthanide comprises La, Ce, Pr and, optionally, Nd. The rare earth A-site dopants preferably comprise La, Nd or a combination thereof, while the alkaline earth A-site dopant preferably comprises Ca. The use of a mixed lanthanide substantially reduces raw material costs in comparison with compositions made from high purity lanthanum starting materials. The amount of the A-site and B-site dopants is controlled in order to provide an air electrode composition having a coefficient of thermal expansion which closely matches that of the other components of the solid oxide fuel cell.

Continuous in vitro exposure of intestinal epithelial cells to E171 food additive causes oxidative stress, inducing oxidation of DNA bases but no endoplasmic reticulum stress.

PubMed

Dorier, Marie; Béal, David; Marie-Desvergne, Caroline; Dubosson, Muriel; Barreau, Frédérick; Houdeau, Eric; Herlin-Boime, Nathalie; Carriere, Marie

2017-08-01

The whitening and opacifying properties of titanium dioxide (TiO 2 ) are commonly exploited when it is used as a food additive (E171). However, the safety of this additive can be questioned as TiO 2 nanoparticles (TiO 2 -NPs) have been classed at potentially toxic. This study aimed to shed some light on the mechanisms behind the potential toxicity of E171 on epithelial intestinal cells, using two in vitro models: (i) a monoculture of differentiated Caco-2 cells and (ii) a coculture of Caco-2 with HT29-MTX mucus-secreting cells. Cells were exposed to E171 and two different types of TiO 2 -NPs, either acutely (6-48 h) or repeatedly (three times a week for 3 weeks). Our results confirm that E171 damaged these cells, and that the main mechanism of toxicity was oxidation effects. Responses of the two models to E171 were similar, with a moderate, but significant, accumulation of reactive oxygen species, and concomitant downregulation of the expression of the antioxidant enzymes catalase, superoxide dismutase and glutathione reductase. Oxidative damage to DNA was detected in exposed cells, proving that E171 effectively induces oxidative stress; however, no endoplasmic reticulum stress was detected. E171 effects were less intense after acute exposure compared to repeated exposure, which correlated with higher Ti accumulation. The effects were also more intense in cells exposed to E171 than in cells exposed to TiO 2 -NPs. Taken together, these data show that E171 induces only moderate toxicity in epithelial intestinal cells, via oxidation.

Chemical evolution of the Earth: Equilibrium or disequilibrium process?

NASA Technical Reports Server (NTRS)

Sato, M.

1985-01-01

To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

Unraveling Recrystallization Mechanisms Governing Texture Development from Rare-Earth Element Additions to Magnesium

NASA Astrophysics Data System (ADS)

Imandoust, Aidin; Barrett, Christopher D.; Al-Samman, Talal; Tschopp, Mark A.; Essadiqi, Elhachmi; Hort, Norbert; El Kadiri, Haitham

2018-03-01

The origin of texture components often associated with rare-earth element (REE) additions in wrought magnesium alloys is a long-standing problem in magnesium technology. While their influence on the texture is unquestionable, it is not yet clear why certain texture components, such as < 11\\bar{2}1 > ||{extrusion}{direction}, are favored over other components typically observed in traditional magnesium alloys. The objective of this research is to identify the mechanisms accountable for these RE textures during early stages of recrystallization. Electron backscattered diffraction and transmission electron microscopy analyses reveal that REEs in zinc-containing magnesium alloys corroborate discontinuous dynamic recrystallization. REEs promote isotropic growth for all nuclei generated through the bulging mechanism. During nucleation, the effect of REEs on orientation selection was explained by the diversified activity of both < 10\\bar{1}0 > and [0001] Taylor axes in the same grain with a marked preference for [0001] rotations to occur first. During nuclei growth, no growth preference was observed when sufficient REEs are added in the zinc-containing magnesium alloys, instead isotropic nuclei growth across all grain orientations occurs. This phenomenon is attributed to REEs segregating to grain boundaries (GBs), in agreement with prior computational and theoretical results (Barrett et al., Scripta Mater 146:46-50, 2018) that show a more isotropic GB energy and mobility after segregation.

Uderstanding Snowball Earth Deglaciation

NASA Astrophysics Data System (ADS)

Abbot, D. S.

2012-12-01

Earth, a normally clement planet comfortably in its star's habitable zone, suffered global or nearly global glaciation at least twice during the Neoproterozoic era (at about 635 and 710 million years ago). Viewed in the context of planetary evolution, these pan-global glaciations (Snowball Earth events) were extremely rapid, lasting only a few million years. The dramatic effect of the Snowball Earth events on the development of the planet can be seen through their link to rises in atmospheric oxygen and evolutionary innovations. These potential catastrophes on an otherwise clement planet can be used to gain insight into planetary habitability more generally. Since Earth is not currently a Snowball, a sound deglaciation mechanism is crucial for the viability of the Snowball Earth hypothesis. The traditional deglaciation mechanism is a massive build up of CO2 due to reduced weathering during Snowball Earth events until tropical surface temperatures reach the melting point. Once initiated, such a deglaciation might happen on a timescale of only dozens of thousands of years and would thrust Earth from the coldest climate in its history to the warmest. Therefore embedded in Snowball Earth events is an even more rapid and dramatic environmental change. Early global climate model simulations raised doubt about whether Snowball Earth deglaciation could be achieved at a CO2 concentration low enough to be consistent with geochemical data, which represented a potential challenge to the Snowball Earth hypothesis. Over the past few years dust and clouds have emerged as the essential missing additional processes that would allow Snowball Earth deglaciation at a low enough CO2 concentration. I will discuss the dust and cloud mechanisms and the modeling behind these ideas. This effort is critical for the broader implications of Snowball Earth events because understanding the specific deglaciation mechanism determines whether similar processes could happen on other planets.

Properties of an Earth-like planet orbiting a Sun-like star: Earth observed by the EPOXI mission.

PubMed

Livengood, Timothy A; Deming, L Drake; A'hearn, Michael F; Charbonneau, David; Hewagama, Tilak; Lisse, Carey M; McFadden, Lucy A; Meadows, Victoria S; Robinson, Tyler D; Seager, Sara; Wellnitz, Dennis D

2011-11-01

NASA's EPOXI mission observed the disc-integrated Earth and Moon to test techniques for reconnoitering extrasolar terrestrial planets, using the Deep Impact flyby spacecraft to observe Earth at the beginning and end of Northern Hemisphere spring, 2008, from a range of ∼1/6 to 1/3 AU. These observations furnish high-precision and high-cadence empirical photometry and spectroscopy of Earth, suitable as "ground truth" for numerically simulating realistic observational scenarios for an Earth-like exoplanet with finite signal-to-noise ratio. Earth was observed at near-equatorial sub-spacecraft latitude on 18-19 March, 28-29 May, and 4-5 June (UT), in the range of 372-4540 nm wavelength with low visible resolving power (λ/Δλ=5-13) and moderate IR resolving power (λ/Δλ=215-730). Spectrophotometry in seven filters yields light curves at ∼372-948 nm filter-averaged wavelength, modulated by Earth's rotation with peak-to-peak amplitude of ≤20%. The spatially resolved Sun glint is a minor contributor to disc-integrated reflectance. Spectroscopy at 1100-4540 nm reveals gaseous water and carbon dioxide, with minor features of molecular oxygen, methane, and nitrous oxide. One-day changes in global cloud cover resulted in differences between the light curve beginning and end of ≤5%. The light curve of a lunar transit of Earth on 29 May is color-dependent due to the Moon's red spectrum partially occulting Earth's relatively blue spectrum. The "vegetation red edge" spectral contrast observed between two long-wavelength visible/near-IR bands is ambiguous, not clearly distinguishing between the verdant Earth diluted by cloud cover versus the desolate mineral regolith of the Moon. Spectrophotometry in at least one other comparison band at short wavelength is required to distinguish between Earth-like and Moon-like surfaces in reconnaissance observations. However, measurements at 850 nm alone, the high-reflectance side of the red edge, could be sufficient to

Tissue deposition and toxicological effects of commercially significant rare earth oxide nanomaterials: Material and physical properties.

PubMed

Das, Soumen; Reed McDonagh, Philip; Selvan Sakthivel, Tamil; Barkam, Swetha; Killion, Kelsey; Ortiz, Julian; Saraf, Shashank; Kumar, Amit; Gupta, Ankur; Zweit, Jamal; Seal, Sudipta

2017-03-01

Rare earth oxide (REO) materials are found naturally in earth's crust and at the nanoscale these REO nanoparticles exhibit unique thermal, electrical, and physicochemical properties. REO nanoparticles are widely used in different industrial sectors for ceramics, glass polishing, metallurgy, lasers, and magnets. Recently, some of these REO nanoparticles have been identified for their potential application in medicine, including therapy, imaging, and diagnostics. Concurrent research into the REO nanomaterials' toxicities has also raised concern for their environmental impacts. The correlation of REO nanoparticles mediated toxicity with their physiochemical properties can help to design nanoparticles with minimal effect on the environment and living organisms. In vitro assay revealed toxicity toward Human squamous epithelial cell line (CCL30) and Human umbilical vascular endothelial cells (HUVEC) at a concentration of 100 µM and higher. In vivo results showed, with the exception of CeO 2 and Gd 2 O 3 , most of the naoparticles did not clear or had minimum clearance (10-20%) from the system. Elevated levels of alanine transferase were seen for animals given each different nanoparticle, however the increases were not significant for CeO 2 and Dy 2 O 3 . Nephrotoxicity was only seen in case of Dy 2 O 3 and Gd 2 O 3 . Lastly, histological examination revealed presence of swollen hepatocytes which further confirms toxicity of the commercial REO nanomaterials. The in vivo toxicity is mainly due to excessive tissue deposition (70-90%) due to the commercial REO nanoparticles' poor physical properties (shape, stability, and extent of agglomeration). Therefore, optimization of nanoparticles physical properties is very important. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 904-917, 2017. © 2016 Wiley Periodicals, Inc.

The oxidation of organic additives in the positive vanadium electrolyte and its effect on the performance of vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Nguyen, Tam D.; Whitehead, Adam; Scherer, Günther G.; Wai, Nyunt; Oo, Moe O.; Bhattarai, Arjun; Chandra, Ghimire P.; Xu, Zhichuan J.

2016-12-01

Despite many desirable properties, the vanadium redox flow battery is limited, in the maximum operation temperature that can be continuously endured, before precipitation begins in the positive electrolyte. Many additives have been proposed to improve the thermal stability of the charged positive electrolyte. However, we have found that the apparent stability, revealed in laboratory testing, is often simply an artifact of the test method and arises from the oxidation of the additive, with corresponding partial reduction of V(V) to V(IV). This does not improve the stability of the electrolyte in an operating system. Here, we examined the oxidation of some typical organic additives with carboxyl, alcohol, and multi-functional groups, in sulfuric acid solutions containing V(V). The UV-vis measurements and titration results showed that many compounds reduced the state-of-charge (SOC) of vanadium electrolyte, for example, by 27.8, 88.5, and 81.9% with the addition of 1%wt of EDTA disodium salt, pyrogallol, and ascorbic acid, respectively. The cell cycling also indicated the effect of organic additives on the cell performance, with significant reduction in the usable charge capacity. In addition, a standard screening method for thermally stable additives was introduced, to quickly screen suitable additives for the positive vanadium electrolyte.

Oxygenic Photosynthesis and the Oxidation State of Mars

NASA Technical Reports Server (NTRS)

Hartman, Hyman; McKay, Christopher P.

1995-01-01

The oxidation state of the Earth's surface is one of the most obvious indications of the effect of life on this planet. The surface of Mars is highly oxidized, as evidenced by its red color, but the connection to life is less apparent. Two possibilities can be considered. First, the oxidant may be photochemically produced in the atmosphere. In this case the fundamental source of O2 is the loss of H2 to space and the oxidant produced is H2O2. This oxidant would accumulate on the surface and thereby destroy any organic material and other reductants to some depth. Recent models suggest that diffusion limits this depth to a few meters. An alternative source of oxygen is biological oxygen production followed by sequestration of organic material in sediments - as on the Earth. In this case, the net oxidation of the surface was determined billions of years ago when Mars was a more habitable planet and oxidative conditions could persist to great depths, over 100 m. Below this must be a compensating layer of biogenic organic material. Insight into the nature of past sources of oxidation on Mars will require searching for organics in the martian subsurface and sediments.

Reduced Gas Cycling in Microbial Mats: Implications for Early Earth

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Bebout, Brad M.; DesMarais, David J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

For more than half the history of life on Earth, biological productivity was dominated by photosynthetic microbial mats. During this time, mats served as the preeminent biological influence on earth's surface and atmospheric chemistry and also as the primary crucible for microbial evolution. We find that modern analogs of these ancient mat communities generate substantial quantities of hydrogen, carbon monoxide, and methane. Escape of these gases from the biosphere would contribute strongly to atmospheric evolution and potentially to the net oxidation of earth's surface; sequestration within the biosphere carries equally important implications for the structure, function, and evolution of anaerobic microbial communities within the context of mat biology.

Records of our Early Biosphere Illuminate our Origins and Guide our Search for Life Beyond Earth

NASA Technical Reports Server (NTRS)

DesMarais, David J.

2003-01-01

A scientific "mission of exploration to early Earth" will help us chart the distribution of life elsewhere. We must discriminate between attributes of biospheres that are universal versus those attributes that represent principally the outcomes of long-term survival specifically on Earth. In addition to the basic physics and chemistry of matter, the geologic evolution of rocky habitable planets and their climates might be similar elsewhere in the Universe. Certain key agents that drive long-term environmental change (e.g., stellar evolution, impacts, geothermal heat flow, tectonics, etc.) can help us to reconstruct ancient climates and to compare their evolution among populations of Earth- like planets. Early Earth was tectonically more active than today and therefore it exhaled reduced chemical species into the more oxidized surface environment at greater rates. This tectonic activity thus sustained oxidation-reduction reactions that provided the basis for the development of biochemical pathways that harvest chemical energy ("bioenergetics"). Most examples of bioenergetics today that extract energy by reacting oxidized and reduced chemicals in the environment were likely more pervasive among our microbial ancestors than are the presently known examples of photosynthesis. The geologic rock record indicates that, as early as 3.5 billion years ago (3.5 Ga), microbial biofilms were widespread within the coastal environments of small continents and tectonically unstable volcanic islands. Non oxygen-producing (non-oxygenic) photosynthesis preceded oxygenic photosynthesis, but all types of photosynthesis contributed substantially to the long-term increase in global primary biological productivity. Evidence of photosynthesis is tentative by 3.5 Ga and compelling by 2.7 Ga. Evidence of oxygenic photosynthesis is strong by 2.7 Ga and compelling by 2.3 Ga. These successive innovations transformed life from local communities that survived principally by catalyzing chemical

Cooking methods employing natural anti-oxidant food additives effectively reduced concentration of nephrotoxic and carcinogenic aristolochic acids in contaminated food grains.

PubMed

Li, Weiwei; Chan, Chi-Kong; Wong, Yee-Lam; Chan, K K Jason; Chan, Ho Wai; Chan, Wan

2018-10-30

Emerging evidence suggests that aristolochic acids (AA) produced naturally by a common weed Aristolochia clematitis in the cultivation fields is contaminating the food products in Balkan Peninsula and acting as the etiological agent in the development of Balkan endemic nephropathy. In this study, we investigated the combined use of natural anti-oxidative "food additives" and different cooking methods to find a solution for the widespread contamination of AA in food products. The results indicated that the addition of healthy dietary supplements (such as cysteine, glutathione, ascorbic acid, citric acid and magnesium) during cooking, is a highly efficient method in lowering the concentration of AA in the final food products. Because previous observation indicated one of the toxicological mechanisms by which AA exert its toxicity is to induce oxidative stress in internal organs, it is anticipated that these added anti-oxidants will also help to attenuate the nephrotoxicity of AA. Copyright © 2018 Elsevier Ltd. All rights reserved.

Crew Earth Observations: Twelve Years of Documenting Earth from the International Space Station

NASA Technical Reports Server (NTRS)

Evans, Cynthia A.; Stefanov, William L.; Willis, Kimberley; Runco, Susan; Wilkinson, M. Justin; Dawson, Melissa; Trenchard, Michael

2012-01-01

The Crew Earth Observations (CEO) payload was one of the initial experiments aboard the International Space Station, and has been continuously collecting data about the Earth since Expedition 1. The design of the experiment is simple: using state-of-the-art camera equipment, astronauts collect imagery of the Earth's surface over defined regions of scientific interest and also document dynamic events such as storms systems, floods, wild fires and volcanic eruptions. To date, CEO has provided roughly 600,000 images of Earth, capturing views of features and processes on land, the oceans, and the atmosphere. CEO data are less rigorously constrained than other remote sensing data, but the volume of data, and the unique attributes of the imagery provide a rich and understandable view of the Earth that is difficult to achieve from the classic remote sensing platforms. In addition, the length-of-record of the imagery dataset, especially when combined with astronaut photography from other NASA and Russian missions starting in the early 1960s, provides a valuable record of changes on the surface of the Earth over 50 years. This time period coincides with the rapid growth of human settlements and human infrastructure.

Evidence for a near-Earth asteroid belt

NASA Technical Reports Server (NTRS)

Rabinowitz, D. L.; Gehrels, T.; Scotti, J. V.; Mcmillan, R. S.; Perry, M. L.; Wisniewski, W.; Larson, S. M.; Howell, E. S.; Mueller, B. E. A.

1993-01-01

In January 1991, the 0.9-m Spacewatch telescope made the first observation of an asteroid outside Earth's atmosphere but in the neighborhood of the Earth-moon system. Since then, more than 40 Earth-approaching asteroids have been discovered, including 13 smaller than 50 m. Using these data, one of us has shown that there is an excess of Earth-approaching asteroids with diameters less than 50 m, relative to the population inferred from the distribution of larger objects. Here we argue that these smaller objects - characterized by low eccentricities, widely ranging inclinations and unusual spectral properties - form a previously undetected asteroid belt concentrated near Earth. The recent discovery of additional small Earth-approaching asteroids supports this conclusion.

Improvements and Additions to NASA Near Real-Time Earth Imagery

NASA Technical Reports Server (NTRS)

Cechini, Matthew; Boller, Ryan; Baynes, Kathleen; Schmaltz, Jeffrey; DeLuca, Alexandar; King, Jerome; Thompson, Charles; Roberts, Joe; Rodriguez, Joshua; Gunnoe, Taylor;

Microanalysis of iron oxidation states in earth and planetary materials

NASA Astrophysics Data System (ADS)

Bajt, S.; Sutton, S. R.; Delaney, J. S.

1995-02-01

Initial studies have been made on quantifying Fe oxidation states in different iron-bearing minerals using K-edge XANES. The energy of a weak pre-edge peak in the XANES spectrum due to 1s-3d electron transition was used to quantify ferric/ferrous ratios with microprobe spatial resolution. The estimated accuracy of the technique was +/- 10% in terms of Fe3+/((Fe2+ + Fe3+)). The detection limit was ~ 100 ppm with a synchrotron beam of ~ 100 μm in diameter. The pre-edge peak energy in well-characterized samples with known Fe oxidation states was found to be a linear function of the ferric/(ferrous) ratio. The technique was applied to altered magnetics (ideally Fe3O4), and various silicates and oxides from meteorites.

Teaching earth science

USGS Publications Warehouse

Alpha, Tau Rho; Diggles, Michael F.

1998-01-01

This CD-ROM contains 17 teaching tools: 16 interactive HyperCard 'stacks' and a printable model. They are separated into the following categories: Geologic Processes, Earthquakes and Faulting, and Map Projections and Globes. A 'navigation' stack, Earth Science, is provided as a 'launching' place from which to access all of the other stacks. You can also open the HyperCard Stacks folder and launch any of the 16 stacks yourself. In addition, a 17th tool, Earth and Tectonic Globes, is provided as a printable document. Each of the tools can be copied onto a 1.4-MB floppy disk and distributed freely.

Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

PubMed

Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

2009-01-01

Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

Loparite, a rare-earth ore (Ce, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3

USGS Publications Warehouse

Hedrick, James B.; Sinha, Shyama P.; Kosynkin, Valery D.

1997-01-01

The mineral loparite (Ce, NA, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3 is the principal ore of the light-group rare-earth elements (LREE) in Russia. The complex oxide has a perovskite (ABO3) structure with coupled substitutions, polymorphism, defect chemistry and a tendency to become metamict. The A site generally contains weakly bonded, easily exchanged cations of the LREE, Na and Ca. The B site generally contains smaller, highly charged cations of Ti, Nb or Fe+3. Mine production is from Russia's Kola Peninsula. Ore is beneficiated to produce a 95% loparite concentrate containing 30% rare-earth oxides. Loparite concentrate is refined by either a chlorination process or acid decomposition process to recover rare-earths, titanium, niobium and tantalum. Rare-earths are separated by solvent extraction and selective precipitation/dissolution. The concentrate is processed at plants in Russia, Estonia and Kazakstan.

Low-Temperature Oxidation Reactions and Cool Flames at Earth and Reduced Gravity

NASA Technical Reports Server (NTRS)

Pearlman, Howard

1999-01-01

Non-isothermal studies of cool flames and low temperature oxidation reactions in unstirred closed vessels are complicated by the perturbing effects of natural convection at earth gravity. Buoyant convection due to self-heating during the course of slow reaction produces spatio-temporal variations in the thermal and thus specie concentration fields due to the Arrhenius temperature dependence of the reaction rates. Such complexities have never been quantitatively modeled and were the primary impetus for the development of CSTR's (continuously stirred tank reactors) 30 years ago. While CSTR's have been widely adopted since they offer the advantage of spatial uniformity in temperature and concentration, all gradients are necessarily destroyed along with any structure that may otherwise develop. Microgravity offers a unique environment where buoyant convection can be effectively minimized and the need for stirring eliminated. Moreover, eliminating buoyancy and the need for stirring eliminates complications associated with the induced hydrodynamic field whose influence on heat transport and hot spot formation, hence explosion limits, is not fully realized. The objective of this research is to quantitatively determine and understand the fundamental mechanisms that control the onset and evolution of low temperature reactions and cool flames in both static and flow reactors. Microgravity experiments will be conducted to obtain benchmark data on the structure (spatio-temporal temperature, concentration, flow fields), the dynamics of the chemical fronts, and the ignition diagrams (pressure vs. temperature). Ground-based experiments will be conducted to ascertain the role of buoyancy. Numerical simulations including detailed kinetics will be conducted and compared to experiment.

Biospheric-atmospheric coupling on the early Earth

NASA Technical Reports Server (NTRS)

Levine, J. S.

1991-01-01

Theoretical calculations performed with a one-dimensional photochemical model have been performed to assess the biospheric-atmospheric transfer of gases. Ozone reached levels to shield the Earth from biologically lethal solar ultraviolet radiation (220-300 nm) when atmospheric oxygen reached about 1/10 of its present atmospheric level. In the present atmosphere, about 90 percent of atmospheric nitrous oxide is destroyed via solar photolysis in the stratosphere with about 10 percent destroyed via reaction with excited oxygen atoms. The reaction between nitrous oxide and excited oxygen atoms leads to the production of nitric oxide in the stratosphere, which is responsible for about 70 percent of the global destruction of oxygen in the stratosphere. In the oxygen/ozone deficient atmosphere, solar photolysis destroyed about 100 percent of the atmospheric nitrous oxide, relegating the production of nitric oxide via reaction with excited oxygen to zero. Our laboratory and field measurements indicate that atmospheric oxygen promotes the biogenic production of N2O and NO via denitrification and the biogenic production of methane by methanogenesis.

Volatiles in the Earth: All shallow and all recycled

NASA Technical Reports Server (NTRS)

Anderson, Don L.

1994-01-01

A case can be made that accretion of the Earth was a high-temperature process and that the primordial Earth was dry. A radial zone-refining process during accretion may have excluded low-melting point and volatile material, including large-ion lithophile elements toward the surface, leaving a refractory and zoned interior. Water, sediments and altered hydrous oceanic crust are introduced back into the interior by subduction, a process that may be more efficient today than in the past. Seismic tomography strongly suggests that a large part of the uppermantle is above the solidus, and this implies wet melting. The mantle beneath Archean cratons has very fast seismic velocities and appears to be strong to 150 km or greater. This is consistent with very dry mantle. It is argued that recycling of substantial quantities of water occurs in the shallow mantle but only minor amounts recycle to depths greater than 200 km. Recycling also oxidizes that mantle; ocean island ('hotspot') basalts are intermediate in oxidation state to island-arc and midocean ridge basalts (MORB). This suggests a deep uncontaminated reservoir for MORB. Plate tectonics on a dry Earth is discussed in order to focus attention on inconsistencies in current geochemical models of terrestrial evolution and recycling.

Semantic Web Data Discovery of Earth Science Data at NASA Goddard Earth Sciences Data and Information Services Center (GES DISC)

NASA Technical Reports Server (NTRS)

Hegde, Mahabaleshwara; Strub, Richard F.; Lynnes, Christopher S.; Fang, Hongliang; Teng, William

2008-01-01

Mirador is a web interface for searching Earth Science data archived at the NASA Goddard Earth Sciences Data and Information Services Center (GES DISC). Mirador provides keyword-based search and guided navigation for providing efficient search and access to Earth Science data. Mirador employs the power of Google's universal search technology for fast metadata keyword searches, augmented by additional capabilities such as event searches (e.g., hurricanes), searches based on location gazetteer, and data services like format converters and data sub-setters. The objective of guided data navigation is to present users with multiple guided navigation in Mirador is an ontology based on the Global Change Master directory (GCMD) Directory Interchange Format (DIF). Current implementation includes the project ontology covering various instruments and model data. Additional capabilities in the pipeline include Earth Science parameter and applications ontologies.

Electro-kinetic Separation of Rare Earth Elements Using a Redox-Active Ligand.

PubMed

Fang, Huayi; Cole, Bren E; Qiao, Yusen; Bogart, Justin A; Cheisson, Thibault; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

2017-10-16

Purification of rare earth elements is challenging due to their chemical similarities. All of the deployed separation methods rely on thermodynamic properties, such as distribution equilibria in solvent extraction. Rare-earth-metal separations based on kinetic differences have not been examined. Herein, we demonstrate a new approach for rare-earth-element separations by exploiting differences in the oxidation rates within a series of rare earth compounds containing the redox-active ligand [{2-(tBuN(O))C 6 H 4 CH 2 } 3 N] 3- . Using this method, a single-step separation factor up to 261 was obtained for the separation of a 50:50 yttrium-lutetium mixture. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

STUDY OF THE EFFECT OF CHLORINE ADDITION ON MERCURY OXIDATION BY SCR CATALYST UNDER SIMULATED SUBBITUMINOUS COAL FLUE GAS

EPA Science Inventory

An entrained flow reactor is used to study the effect of addition of chlorine-containing species on the oxidation of elemental mercury (Hgo)by a selective catalytic reduction (SCR) catalyst in simulated subbituminous coal combustion flue gas. The combustion flue gas was doped wit...

Design of template-stabilized active and earth-abundant oxygen evolution catalysts in acid† †Electronic supplementary information (ESI) available: CVs for unary metal oxides deposition, electrochemical stability at higher current densities for unary metal oxides at pH 2.5, EDS maps for CoMnOx and CoPbOx, STEM images and PXRD of CoMnOx and CoFePbOx, high-resolution XPS of Fe 2p for CoFePbOx, Pourbaix diagrams (of Mn, Co, Pb, and Fe), and elemental analysis. See DOI: 10.1039/c7sc01239j Click here for additional data file.

PubMed Central

Huynh, Michael; Ozel, Tuncay; Liu, Chong; Lau, Eric C.

2017-01-01

Oxygen evolution reaction (OER) catalysts that are earth-abundant and are active and stable in acid are unknown. Active catalysts derived from Co and Ni oxides dissolve at low pH, whereas acid stable systems such as Mn oxides (MnOx) display poor OER activity. We now demonstrate a rational approach for the design of earth-abundant catalysts that are stable and active in acid by treating activity and stability as decoupled elements of mixed metal oxides. Manganese serves as a stabilizing structural element for catalytically active Co centers in CoMnOx films. In acidic solutions (pH 2.5), CoMnOx exhibits the OER activity of electrodeposited Co oxide (CoOx) with a Tafel slope of 70–80 mV per decade while also retaining the long-term acid stability of MnOx films for OER at 0.1 mA cm–2. Driving OER at greater current densities in this system is not viable because at high anodic potentials, Mn oxides convert to and dissolve as permanganate. However, by exploiting the decoupled design of the catalyst, the stabilizing structural element may be optimized independently of the Co active sites. By screening potential–pH diagrams, we replaced Mn with Pb to prepare CoFePbOx films that maintained the high OER activity of CoOx at pH 2.5 while exhibiting long-term acid stability at higher current densities (at 1 mA cm–2 for over 50 h at pH 2.0). Under these acidic conditions, CoFePbOx exhibits OER activity that approaches noble metal oxides, thus establishing the viability of decoupling functionality in mixed metal catalysts for designing active, acid-stable, and earth-abundant OER catalysts. PMID:29163926

Earth as art 4

USGS Publications Warehouse

,

2016-03-29

Landsat 8 is the latest addition to the long-running series of Earth-observing satellites in the Landsat program that began in 1972. The images featured in this fourth installment of the Earth As Art collection were all acquired by Landsat 8. They show our planet’s diverse landscapes with remarkable clarity.Landsat satellites see the Earth as no human can. Not only do they acquire images from the vantage point of space, but their sensors record infrared as well as visible wavelengths of light. The resulting images often reveal “hidden” details of the Earth’s land surface, making them invaluable for scientific research.As with previous Earth As Art exhibits, these Landsat images were selected solely for their aesthetic appeal. Many of the images have been manipulated to enhance color variations or details. They are not intended for scientific interpretation—only for your viewing pleasure. What do you see in these unique glimpses of the Earth’s continents, islands, and coastlines?

Investigation of gamma ray shielding efficiency and mechanical performances of concrete shields containing bismuth oxide as an environmentally friendly additive

NASA Astrophysics Data System (ADS)

Yao, Ya; Zhang, Xiaowen; Li, Mi; Yang, Rong; Jiang, Tianjiao; Lv, Junwen

2016-10-01

Concrete has a proven ability to attenuate gamma rays and neutrons without compromising structural property; therefore, it is widely used as the primary shielding material in many nuclear facilities. Recently, there is a tendency toward using various additives to enhance the shielding properties of these concrete mixtures. However, most of these additives being used either pose hygiene hazards or require special handling processes. It would be ideal if environmentally friendly additives were available for use. The bismuth oxide (Bi2O3) additive shows promise in various shielding applications due to its proven radiation attenuation ability and environmentally friendly nature. To the best of our knowledge, however, Bi2O3 has never been used in concrete mixtures. Therefore, for this research, we fabricated the Bi2O3-based concrete mixtures by adding Bi2O3 powder in the ordinary concrete mixture. Concrete mixtures with lead oxide (PbO) additives were used for comparison. Radiation shielding parameters like the linear attenuation coefficients (LAC) of all these concrete mixtures showing the effects of the Bi2O3 additions are presented. The mechanical performances of concrete mixtures incorporated with Bi2O3 additive were also investigated. It suggested that the concrete mixture containing 25% Bi2O3 powder (B5 in this study) provided the best shielding capacity and mechanical performance among other mixes. It has a significant potential for application as a structural concrete where radiological protection capability is required.

Thermal, dynamic and compositional aspects of the core-forming Earth

NASA Technical Reports Server (NTRS)

Stevenson, D. J.

1985-01-01

Core formation is the most important and singular differentiation event in the history of a terrestrial planet. It almost certainly involved the downward migration of a partially or wholly molten iron alloy through a silicate and oxide mantle, and was contemporaneous with accretion. Several important, unresolved issues which have implications for mantle and core geochemistry, the thermal history of the Earth, and the origin of geomagnetism are addressed: whether the early Earth was molten; whether core formation involved low or high pressure geochemistry, or both; early Earth mantle homogenization; whether equilibration established between core forming material and the mantle through which it migrated; and how much iron is stranded and unable to reach the core.

Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the O2 addition reaction pathways.

PubMed

Shiroudi, A; Deleuze, M S; Canneaux, S

2015-05-28

Atmospheric oxidation of the naphthalene-OH adduct [C10H8OH]˙ (R1) by molecular oxygen in its triplet electronic ground state has been studied using density functional theory along with the B3LYP, ωB97XD, UM05-2x and UM06-2x exchange-correlation functionals. From a thermodynamic viewpoint, the most favourable process is O2 addition at the C2 position in syn mode, followed by O2 addition at the C2 position in anti mode, O2 addition at the C4 position in syn mode, and O2 addition at the C4 position in anti mode, as the second, third and fourth most favourable processes. The syn modes of addition at these positions are thermodynamically favoured over the anti ones by the formation of an intramolecular hydrogen bond between the hydroxyl and peroxy substituents. Analysis of the computed structures, bond orders and free energy profiles demonstrate that the reaction steps involved in the oxidation of the naphthalene-OH adduct by O2 satisfy Hammond's principle. Kinetic rate constants and branching ratios under atmospheric pressure and in the fall-off regime have been supplied, using transition state and RRKM theories. By comparison with experiment, these data confirm the relevance of a two-step reaction mechanism. Whatever the addition mode, O2 addition in C4 position is kinetically favoured over O2 addition in C2 position, in contrast with the expectations drawn from thermodynamics and reaction energies. Under a kinetic control of the reaction, and in line with the computed reaction energy barriers, the most efficient process is O2 addition at the C4 position in syn mode, followed by O2 addition at the C2 position in syn mode, O2 addition at the C4 position in anti mode, and O2 addition at the C2 position in anti mode as the second, third and fourth most rapid processes. The computed branching ratios also indicate that the regioselectivity of the reaction decreases with increasing temperatures and decreasing pressures.

Implications of Δ33S for Evolution of Earth's Sulfur Cycle and Atmosphere

NASA Astrophysics Data System (ADS)

Farquhar, J.; Wing, B. A.

2002-12-01

The recent observation of large magnitude Δ33S anomalies in parts of the rock record has changed the way that we view the sulfur cycle. On the basis of Δ33S we can divide the sulfur cycle into three distinct phases - an Archean phase, an early Paleoproterozoic phase, and a modern phase. The occurrence of large magnitude Δ33S anomalies in rocks of Archean age (>2.45 Ga) is attributed to deep UV photolysis of sulfur dioxide in an atmosphere that was largely anoxic with <= 10-5 PAL O2. The presence of multiple exit channels for both oxidized and reduced atmospheric sulfur allowed efficient transfer of sulfur isotope anomalies to the Earth's surface reservoirs under these conditions (see Pavlov and Kasting, 2002). The absence of an active cycle of surface oxidation and bacterial (?) sulfate reduction insured preservation of the anomalies in the rock record. During the early Paleoproterozoic (<2.45 Ga but > 2.1 Ga) the occurrence of isotopic anomalies with substantially smaller magnitudes points to an atmosphere with higher but probably still diminutive levels of oxygen. As suggested by variations in Δ33S associated with rocks representing global glacial intervals, oxygen levels were probably fluctuating during this interval and reflect the preference of Earth's atmosphere for either a stable reduced or oxidized state. The absence of measurable anomalies in the rock record after 2.1 Ga points to an atmosphere that has been largely oxidized (> 10-5 to 10-2 PAL O2) since then. New Δ33S data from a variety of terrestrial rock samples provide unique insights into the nature of Earth's early surface environment and allow well-constrained speculation about the evolution of Earth's sulfur cycle.

Air electrode composition for solid oxide fuel cell

DOEpatents

Kuo, L.; Ruka, R.J.; Singhal, S.C.

1999-08-03

An air electrode composition for a solid oxide fuel cell is disclosed. The air electrode material is based on lanthanum manganite having a perovskite-like crystal structure ABO{sub 3}. The A-site of the air electrode composition comprises a mixed lanthanide in combination with rare earth and alkaline earth dopants. The B-site of the composition comprises Mn in combination with dopants such as Mg, Al, Cr and Ni. The mixed lanthanide comprises La, Ce, Pr and, optionally, Nd. The rare earth A-site dopants preferably comprise La, Nd or a combination thereof, while the alkaline earth A-site dopant preferably comprises Ca. The use of a mixed lanthanide substantially reduces raw material costs in comparison with compositions made from high purity lanthanum starting materials. The amount of the A-site and B-site dopants is controlled in order to provide an air electrode composition having a coefficient of thermal expansion which closely matches that of the other components of the solid oxide fuel cell. 3 figs.

Data on the surface morphology of additively manufactured Ti-6Al-4V implants during processing by plasma electrolytic oxidation.

PubMed

van Hengel, Ingmar A J; Riool, Martijn; Fratila-Apachitei, Lidy E; Witte-Bouma, Janneke; Farrell, Eric; Zadpoor, Amir A; Zaat, Sebastian A J; Apachitei, Iulian

2017-08-01

Additively manufactured Ti-6Al-4V implants were biofunctionalized using plasma electrolytic oxidation. At various time points during this process scanning electron microscopy imaging was performed to analyze the surface morphology (van Hengel et al., 2017) [1]. This data shows the changes in surface morphology during plasma electrolytic oxidation. Data presented in this article are related to the research article "Selective laser melting porous metallic implants with immobilized silver nanoparticles kill and prevent biofilm formation by methicillin-resistant Staphylococcus aureus" (van Hengel et al., 2017) [1].

Metal- and Additive-Free Oxidation of Sulfides into Sulfoxides by Fullerene-Modified Carbon Nitride with Visible-Light Illumination.

PubMed

Chen, Xi; Deng, Kejian; Zhou, Peng; Zhang, Zehui

2018-05-24

Photocatalytic selective oxidation has attracted considerable attention as an environmentally friendly strategy for organic transformations. Some methods have been reported for the photocatalytic oxidation of sulfides into sulfoxides in recent years. However, the practical application of these processes is undermined by several challenges, such as low selectivity, sluggish reaction rates, the requirement of UV-light irradiation, the use of additives, and the instability of the photocatalyst. Herein, a metal-free C 60 /graphitic carbon nitride (g-C 3 N 4 ) composite photocatalyst was fabricated by a facile method, and well characterized by TEM, SEM, FTIR spectroscopy, XRD, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The C 60 /g-C 3 N 4 catalyst exhibited a high photocatalytic activity at room temperature for the selective oxidation of sulfides into the corresponding sulfoxides in the presence of other functional groups, due to the synergetic roles of C 60 and g-C 3 N 4 . Several important parameters have been screened, and this method afforded good to excellent yields of sulfoxides under optimal conditions. The superoxide radical ( . O 2 - ) and singlet oxygen ( 1 O 2 ) were identified as the oxidative species for the oxidation of sulfides into sulfoxides by exploring EPR experiments, and hence, a plausible mechanism for this oxidation was proposed. Moreover, the C 60 /g-C 3 N 4 catalyst can be easily recovered by filtration and then reused at least four times without loss in activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Earth retaining structures manual

DOT National Transportation Integrated Search

2009-10-29

The objectives of this policy are to obtain statewide uniformity, establish standard : procedures and delineate responsibility for the preparation and review of plans, : design and construction control of earth retaining structures. In addition, it i...

Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates.

PubMed

Zhang, Miao; Frei, Heinz

2017-05-05

Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. Combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

Effect of RE (Nd3+, Sm3+) oxide on structural, optical properties of Na2O-Li2O-ZnO-B2O3 glass system

NASA Astrophysics Data System (ADS)

Hivrekar, Mahesh M.; Bhoyar, D. N.; Mande, V. K.; Dhole, V. V.; Solunke, M. B.; Jadhav, K. M.

2018-05-01

Zinc borate glass activated with rare earth oxide (Nd2O3, Sm2O3) of Na2O-Li2O-ZnO-B2O3 quaternary system has been prepared successfully by melt quenching method. The nucleation and growth of RE oxide were controlled temperature range 950-1000° C and rapid cooling at room temperature. The physical, structural and optical properties were characterized by using X-ray diffraction (XRD), SEM, Ultraviolet-visible spectroscopy (UV-Vis). XRD and SEM studies confirmed the amorphous nature, surface morphology of prepared zinc borate glass. The physical parameters like density, molar volume, molar mass of Nd3+, Sm3+ doped borate glass are summarized in the present article. The optical absorption spectra along with tauc's plot are presented. The optical energy band gap increases due to the addition of rare earth oxide confirming the role of network modifier.

Complete regioselective addition of grignard reagents to pyrazine N-oxides, toward an efficient enantioselective synthesis of substituted piperazines.

PubMed

Andersson, Hans; Banchelin, Thomas Sainte-Luce; Das, Sajal; Gustafsson, Magnus; Olsson, Roger; Almqvist, Fredrik

2010-01-15

A conceptually new one-pot strategy for the synthesis of protected substituted piperazines via the addition of Grignard reagents to pyrazine N-oxides is presented. This strategy is high yielding (33-91% over three steps), step-efficient, and fast. The synthesized N,N-diprotected piperazines are convenient to handle and allow for orthogonal deprotection at either nitrogen for selective transformations. In addition, this is a synthetic route to enantiomerically enriched piperazines by using a combination of phenyl magnesium chloride and (-)-sparteine, which resulted in enantiomeric excesses up to 83%.

Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

NASA Astrophysics Data System (ADS)

Francillon, Wesley

This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is

Elasticity of Deep-Earth Materials at High P and T: Implication for Earths Lower Mantle

NASA Astrophysics Data System (ADS)

Bass, Jay; Sinogeikin, S. V.; Mattern, Estelle; Jackson, J. M.; Matas, J.; Wang, J.; Ricard, Y.

2005-03-01

Brillouin spectroscopy allows measurements of sound velocities and elasticity on phases of geophysical interest at high Pressures and Temperatures. This technique was used to measure the properties of numerous important phases of Earths deep interior. Emphasis is now on measurements at elevated P-T conditions, and measurements on dense polycrystals. Measurements to 60 GPa were made using diamond anvil cells. High temperature is achieved by electrical resistance and laser heating. Excellent results are obtained for polycrystalline samples of dense oxides such as silicate spinels, and (Mg,Al)(Si,Al)O3 --perovskites. A wide range of materials can now be characterized. These and other results were used to infer Earths average lower mantle composition and thermal structure by comparing mineral properties at lower mantle P-T conditions to global Earth models. A formal inversion procedure was used. Inversions of density and bulk sound velocity do not provide robust compositional and thermal models. Including shear properties in the inversions is important to obtain unique solutions. We discuss the range of models consistent with present lab results, and data needed to further refine lower mantle models.

Cathodoluminescent characteristics and light technical parameters of thin-film screens based on oxides and oxysulfides of rare-earth elements

NASA Astrophysics Data System (ADS)

Bondar, Vyacheslav D.; Grytsiv, Myroslav; Groodzinsky, Arkady; Vasyliv, Mykhailo

1995-11-01

Results on creation of thin-film single-crystal high-resolution screens with energy control of luminescence color are presented. In order to create phosphor films ion-plasma technology for deposition of yttrium and lanthanum oxides and oxysulfides activated by rare earth elements has been developed. The screen consists of phosphor film on phosphor substrate with different colors of luminescence (e.g. Y2O3-Eu film with red color on Y3Al5O12- Tb, Ce substrate with green color of luminescence). Electron irradiation causes luminescence with color that depends on energy of the electron beam. The physical reason for color change is that electron beam energy defines electron penetration depth. If the energy is weak, only the film is excited. More powerful beam penetrates into the substrate and thus changes the color of luminescence.

Thermodynamic properties of some metal oxide-zirconia systems

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.

1989-01-01

Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

Enhanced NO2 abatement by alkaline-earth modified g-C3N4 nanocomposites for efficient air purification

NASA Astrophysics Data System (ADS)

Papailias, Ilias; Todorova, Nadia; Giannakopoulou, Tatiana; Karapati, Sofia; Boukos, Nikos; Dimotikali, Dimitra; Trapalis, Christos

2018-02-01

The emission of nitrogen dioxide (NO2) is a major problem encountered in photocatalytic NOx removal for air purification. Although the oxidation of nitric oxide (NO) has been extensively studied, the elimination of NO2 byproduct is still in preliminary stage. In this work, alkaline-earth modified graphitic carbon nitride (g-C3N4) is proposed for efficient NOx removal by minimizing the emission of NO2 during the NO oxidation process. The novel photocatalysts were synthesized by annealing mixtures of melamine and various alkaline-earth acetates (magnesium, calcium and barium acetate) at 550 °C for 3 h. The specific surface area of the photocatalysts varied between 4.65 and 11.81 m2/g. The formation of MgO, CaCO3 and BaCO3 was demonstrated by XPS and FT-IR analyses. The initial concentration of each alkaline-earth precursor was 5 and 10 wt%, while the final metal concentration in the nanocomposites was in the range of 7.19-22.39 wt%. The modified photocatalysts showed slightly reduced NO oxidation ability. However, the overall air quality was significantly improved by restraining the NO2 emission. The results were related to the basic character of the nanocomposites due to the presence of alkaline-earths and their enhanced NO2 adsorption capability.

EarthRef.org: Exploring aspects of a Cyber Infrastructure in Earth Science and Education

NASA Astrophysics Data System (ADS)

Staudigel, H.; Koppers, A.; Tauxe, L.; Constable, C.; Helly, J.

2004-12-01

EarthRef.org is the common host and (co-) developer of a range of earth science databases and IT resources providing a test bed for a Cyberinfrastructure in Earth Science and Education (CIESE). EarthRef.org data base efforts include in particular the Geochemical Earth Reference Model (GERM), the Magnetics Information Consortium (MagIC), the Educational Resources for Earth Science Education (ERESE) project, the Seamount Catalog, the Mid-Ocean Ridge Catalog, the Radio-Isotope Geochronology (RiG) initiative for CHRONOS, and the Microbial Observatory for Fe oxidizing microbes on Loihi Seamount (FeMO; the most recent development). These diverse databases are developed under a single database umbrella and webserver at the San Diego Supercomputing Center. All the data bases have similar structures, with consistent metadata concepts, a common database layout, and automated upload wizards. Shared resources include supporting databases like an address book, a reference/publication catalog, and a common digital archive making database development and maintenance cost-effective, while guaranteeing interoperability. The EarthRef.org CIESE provides a common umbrella for synthesis information as well as sample-based data, and it bridges the gap between science and science education in middle and high schools, validating the potential for a system wide data infrastructure in a CIESE. EarthRef.org experiences have shown that effective communication with the respective communities is a key part of a successful CIESE facilitating both utility and community buy-in. GERM has been particularly successful at developing a metadata scheme for geochemistry and in the development of a new electronic journal (G-cubed) that has made much progress in data publication and linkages between journals and community data bases. GERM also has worked, through editors and publishers, towards interfacing databases with the publication process, to accomplish a more scholarly and database friendly data

Some Mineral Physics Observations Pertinent to the Rheological Properties of Super-Earths

NASA Astrophysics Data System (ADS)

Karato, S.

2010-12-01

Both orbital and thermal evolution of recently discovered super-Earths (terrestrial planets whit mass exceeding that of Earth) depends critically on the rheological properties of their mantle. Although direct experimental studies on rheological properties are unavailable under the conditions equivalent to the deep mantles of these planets (~1 TPa and ~5000 K), a review of key materials science observations suggests that the deep mantle of these planets have much lower viscosity than most of the shallower regions of these planets. The key observations are: (i) phase transformations likely occur under these conditions including the B1 to B2 transition in MgO (1) and the dissociation of MgSiO3 into two oxides (MgO and SiO2) (2), (ii) the systematics in high-temperature creep show that materials with NaCl (B1) structures have much smaller viscosity than other oxides compared at the same normalized conditions (3), and (iii) diffusion coefficients in most of materials have a minimum at certain pressure and above that pressure it increases with pressure (due to mechanism transition) (4). In addition, a review of existing studies also shows that the ionic solids with B2 (CsCl) structure have larger diffusion coefficients than their B1 counter parts. Furthermore, if metallization transition occurs in any of these materials, delocalized electrons will further weaken the material. All of these observations or concepts suggest that even though the viscosity of a planet (below the asthenosphere) increases with depth in the relatively shallow regions, viscosity likely starts to decrease with depth below some critical depth (>~2000 km). The inferred low viscosity of super-Earths implies a large tidal dissipation and relatively rapid orbital evolution. Also such a rheological properties likely promote a layered mantle convection that enhances a weak deep mantle and retards the thermal evolution. 1. A. R. Oganov, M. J. Gillan, G. D. Price, Journal of Chemical Physics 118, 10174

Mineral remains of early life on Earth? On Mars?

USGS Publications Warehouse

Iberall, Robbins E.; Iberall, A.S.

1991-01-01

The oldest sedimentary rocks on Earth, the 3.8-Ga Isua Iron-Formation in southwestern Greenland, are metamorphosed past the point where organic-walled fossils would remain. Acid residues and thin sections of these rocks reveal ferric microstructures that have filamentous, hollow rod, and spherical shapes not characteristic of crystalline minerals. Instead, they resemble ferric-coated remains of bacteria. Because there are no earlier sedimentary rocks to study on Earth, it may be necessary to expand the search elsewhere in the solar system for clues to any biotic precursors or other types of early life. A study of morphologies of iron oxide minerals collected in the southern highlands during a Mars sample return mission may therefore help to fill in important gaps in the history of Earth's earliest biosphere. -from Authors

Layer growth kinetics and wear resistance of martensitic precipitation hardening stainless steel plasma nitrocarburized at 460°C with rare earth addition

NASA Astrophysics Data System (ADS)

Liu, R. L.; Qiao, Y. J.; Yan, M. F.; Fu, Y. D.

2013-09-01

To study the effect of rare earth (RE) addition on low temperature plasma nitrocarburizing of martensitic precipitation hardening stainless steel, 17-4PH stainless steel was plasma nitrocarburized at 460 °C for different times with RE addition. The modified layers were tested by optical microscope, scanning electron microscope, X-ray diffraction, microhardness tester and pin-on-disc tribometer. The experimental results show that the layer depth of plasma RE nitrocarburized layer can be increased up to 56% compared with plasma nitrocarburizing without RE addition. Incorporation of RE element is beneficial to the formation of nitrogen and carbon expanded martensite (α'N). The surface microhardness of plasma RE nitrocarburized layer can be increased to 1286 HV and higher up to 80 HV than that obtained from the conventional treated one. The friction coefficient of martensitic stainless steel can be dramatically decreased by low temperature plasma nitrocarburizing with RE addition, and the friction coefficient of the modified specimens decrease gradually with increasing process time in the present test condition.

Un-Earth-like interiors of the Earth-like planets

NASA Astrophysics Data System (ADS)

Shim, S. H. D.; Nisr, C.; Pagano, M.; Chen, H.; Ko, B.; Noble, S.; Leinenweber, K. D.; Young, P.; Desch, S. J.

2015-12-01

A number of exoplanets have been described as "Earth-like" planets (or even exo-earths) based on the mass-radius relations. Yet, significant variations have been documented in elemental abundances of planet-hosting stars, which will result in very different structures and processes in the interiors of rocky exoplanets. Recent data suggest that the Mg/Si ratio can be as small as less than 1 and as large as more than 2, opening the possibilities for the upper mantles to be dominated by pyroxene and olivine, respectively, and the lower mantles to be dominated by bridgmanite and ferropericlase, respectively. The changes in mineralogy will alter key properties, such as discontinuity structures (and therefore scale of mantle mixing), viscosity, and volatiles storage, of the mantle. Partial melting of such mantles would result in different compositions of the crusts, affecting the tectonics. However, the prediction should be made carefully because oxygen fugacity and contents of volatiles can change the mineralogy even for the same bulk composition. In extremely reducing proto-planetary disks, carbides will form instead of oxides and silicates, and become main constituents of planets in the system. Because carbides have high thermal conductivity and low thermal expansivity, internal heat transport of such planets may be dominated by conduction and mantle mixing would be much more limited than that of the Earth. However, the behaviors and properties of carbides need to be understood better at high pressure and high temperature. Some rocky exoplanets may have very thick layers of water and other icy materials. Interactions between ice (or fluid) and rock at extreme conditions would be the key to understand dynamics and habitability of such exoplanets.

Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes: Oxide Solubility Determinations

NASA Astrophysics Data System (ADS)

Martinez, Ana Maria; Støre, Anne; Osen, Karen Sende

2018-04-01

Electrolytic production of light rare earth elements and alloys takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds, and side cathode reactions could largely be minimized by a good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The oxide content of the fluoride melts REF3-LiF (RE = Nd, Dy) at different compositions and temperatures were experimentally determined by carbothermal analysis of melt samples. The highest solubility values of oxide species, added as Dy2O3 and Dy2(CO3)3, were obtained to be of ca. 3 wt pct (expressed as Dy2O3) in the case of the equimolar DyF3-LiF melt at 1323 K (1050 °C). The oxide saturation values increased with the amount of REF3 present in the molten bath and the working temperature.

Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

PubMed

Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

2015-10-14

Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

The Obtaining of Nano Oxide Systems SiO2-REE with Alkoxide Technology

NASA Astrophysics Data System (ADS)

Amelina, Anna; Grinberg, Evgenii

A lot of oxides systems with REE as dopants are used in catalytic processes in organic synthesis. They are very perspectives as thermostable coating in aerospace technics. These systems are usually based on silicon or aluminium oxides and doped with rare-earth elements. This systems can be produced by different methods. One of the most perspective of them is “sol-gel”-method with silicium, aluminium and rare-earth alkoxides as a precursor of doped silica and alumina, or their derivatives. Thus the obtaining of composite SiO _{2} - REE oxide materials by the hydrolysis doped with rare-earth elements was suggested. Some of alcoholate derivatives such as El(OR)n were used in this processes. The SiO _{2}- REE oxides were precipitated during the sol-gel process, where tetraethoxysilane (TEOS) as used as SiO _{2} sources. Also it is known that alkoxides of alkali metals, including lithium alkoxides, are widely used in industry and synthetic chemistry, as well as a source of lithium in various mixed oxide compositions, such as lithium niobate, lithium tantalate or lithium silicate. Therefore, we attempted to obtain the lithium silicate, which is also doped with rare-earth elements. Lithium silicate was obtained by alkaline hydrolysis of tetraethoxysilane with lithium alkoxide. Lithium alkoxide were synthesized by dissolving at metal in the corresponding alcohol are examined. The dependence of the rate of dissolving of the metal on the method of mixing of the reaction mixture and the degree of metal dispersion was investigated. The mathematical model of the process was composed and also optimization of process was carried out. Some oxide SiO _{2}, Al _{2}O _{3} and rare-earth nanostructured systems were obtained by sol-gel-method. The size of particle was determined by electron and X-ray spectroscopy and was in the range of 5 - 15 nm. Purity of this oxide examples for contaminating of heavy metals consists n.(1E-4...1E-5) wt%. Sols obtained by this method may be used

Hydrogen plasma treatment for improved conductivity in amorphous aluminum doped zinc tin oxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morales-Masis, M., E-mail: monica.moralesmasis@epfl.ch; Ding, L.; Dauzou, F.

2014-09-01

Improving the conductivity of earth-abundant transparent conductive oxides (TCOs) remains an important challenge that will facilitate the replacement of indium-based TCOs. Here, we show that a hydrogen (H{sub 2})-plasma post-deposition treatment improves the conductivity of amorphous aluminum-doped zinc tin oxide while retaining its low optical absorption. We found that the H{sub 2}-plasma treatment performed at a substrate temperature of 50 °C reduces the resistivity of the films by 57% and increases the absorptance by only 2%. Additionally, the low substrate temperature delays the known formation of tin particles with the plasma and it allows the application of the process to temperature-sensitivemore » substrates.« less

Interaction of Metal Oxides with Biomolecules: Implication in Astrobiology

NASA Astrophysics Data System (ADS)

Kamaluddin; Iqubal, Md. Asif

2014-08-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Polymerization of biomonomers could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

An Analysis of Earth Science Data Analytics Use Cases

NASA Technical Reports Server (NTRS)

Shie, Chung-Lin; Kempler, Steve

2014-01-01

The increase in the number and volume, and sources, of globally available Earth science data measurements and datasets have afforded Earth scientists and applications researchers unprecedented opportunities to study our Earth in ever more sophisticated ways. In fact, the NASA Earth Observing System Data Information System (EOSDIS) archives have doubled from 2007 to 2014, to 9.1 PB (Ramapriyan, 2009; and https:earthdata.nasa.govaboutsystem-- performance). In addition, other US agency, international programs, field experiments, ground stations, and citizen scientists provide a plethora of additional sources for studying Earth. Co--analyzing huge amounts of heterogeneous data to glean out unobvious information is a daunting task. Earth science data analytics (ESDA) is the process of examining large amounts of data of a variety of types to uncover hidden patterns, unknown correlations and other useful information. It can include Data Preparation, Data Reduction, and Data Analysis. Through work associated with the Earth Science Information Partners (ESIP) Federation, a collection of Earth science data analytics use cases have been collected and analyzed for the purpose of extracting the types of Earth science data analytics employed, and requirements for data analytics tools and techniques yet to be implemented, based on use case needs. ESIP generated use case template, ESDA use cases, use case types, and preliminary use case analysis (this is a work in progress) will be presented.

Rare earth elements and permanent magnets (invited)

NASA Astrophysics Data System (ADS)

Dent, Peter C.

2012-04-01

Rare earth (RE) magnets have become virtually indispensible in a wide variety of industries such as aerospace, automotive, electronics, medical, and military. RE elements are essential ingredients in these high performance magnets based on intermetallic compounds RECo5, RE2TM17 (TM: transition metal), and RE2TM14B. Rare earth magnets are known for their superior magnetic properties—high induction, and coercive force. These properties arise due to the extremely high magnetocrystalline anisotropy made possible by unique 3d-4f interactions between transition metals and rare earths. For more than 40 years, these magnets remain the number one choice in applications that require high magnetic fields in extreme operating conditions—high demagnetization forces and high temperature. EEC produces and specializes in RECo5 and RE2TM17 type sintered magnets. Samarium and gadolinium are key RE ingredients in the powder metallurgical magnet production processes which include melting, crushing, jet milling, pressing, sintering, and heat treating. The magnetic properties and applications of these magnets will be discussed. We will also briefly discuss the past, current, and future of the permanent magnet business. Currently, over 95% of all pure rare earth oxides are sourced from China, which currently controls the market. We will provide insights regarding current and potential new magnet technologies and designer choices, which may mitigate rare earth supply chain issues now and into the future.

Recovery of rare earths from spent NdFeB magnets of wind turbine: Leaching and kinetic aspects.

PubMed

Kumari, Aarti; Sinha, Manish Kumar; Pramanik, Swati; Sahu, Sushanta Kumar

2018-05-01

Increasing demands of rare earth (RE) metals for advanced technological applications coupled with the scarcity of primary resources have led to the development of processes to treat secondary resources like scraps or end of life products that are often rich in such metals. Spent NdFeB magnet may serve as a potential source of rare earths containing around ∼30% of neodymium and other rare earths. In the present investigation, a pyro-hydrometallurgical process has been developed to recover rare earth elements (Nd, Pr and Dy) from the spent wind turbine magnet. The spent magnet is demagnetized and roasted at 1123 K to convert rare earths and iron to their respective oxides. Roasting of the magnet not only provides selectivity, but enhances the leaching efficiency also. The leaching of the roasted sample with 0.5 M hydrochloric acid at 368 K, 100 g/L pulp density and 500 rpm for 300 min selectively recovers the rare earth elements almost quantitatively leaving iron oxide in the residue. Leaching of rare earth elements with hydrochloric acid follows the mixed controlled kinetic model with activation energy (E a ) of 30.1 kJ/mol in the temperature range 348-368 K. The leaching mechanism is further established by characterizing the leach residues obtained at different time intervals by scanning electron microscopy- energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Individual rare earth elements from the leach solution containing 16.8 g/L of Nd, 3.8 g/L Pr, 0.28 g/L of Dy and other minor impurity elements could be separated by solvent extraction. However, mixed rare earth oxide of 99% purity was produced by oxalate precipitation followed by roasting. The leach residue comprising of pure hematite has a potential to be used as pigment or can find other applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of the addition of low rare earth elements (lanthanum, neodymium, cerium) on the biodegradation and biocompatibility of magnesium.

PubMed

Willbold, Elmar; Gu, Xuenan; Albert, Devon; Kalla, Katharina; Bobe, Katharina; Brauneis, Maria; Janning, Carla; Nellesen, Jens; Czayka, Wolfgang; Tillmann, Wolfgang; Zheng, Yufeng; Witte, Frank

2015-01-01

Rare earth elements are promising alloying element candidates for magnesium alloys used as biodegradable devices in biomedical applications. Rare earth elements have significant effects on the high temperature strength as well as the creep resistance of alloys and they improve magnesium corrosion resistance. We focused on lanthanum, neodymium and cerium to produce magnesium alloys with commonly used rare earth element concentrations. We showed that low concentrations of rare earth elements do not promote bone growth inside a 750 μm broad area around the implant. However, increased bone growth was observed at a greater distance from the degrading alloys. Clinically and histologically, the alloys and their corrosion products caused no systematic or local cytotoxicological effects. Using microtomography and in vitro experiments, we could show that the magnesium-rare earth element alloys showed low corrosion rates, both in in vitro and in vivo. The lanthanum- and cerium-containing alloys degraded at comparable rates, whereas the neodymium-containing alloy showed the lowest corrosion rates. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Volatile accretion history of the Earth.

PubMed

Wood, B J; Halliday, A N; Rehkämper, M

2010-10-28

It has long been thought that the Earth had a protracted and complex history of volatile accretion and loss. Albarède paints a different picture, proposing that the Earth first formed as a dry planet which, like the Moon, was devoid of volatile constituents. He suggests that the Earth's complement of volatile elements was only established later, by the addition of a small veneer of volatile-rich material at ∼100 Myr (here and elsewhere, ages are relative to the origin of the Solar System). Here we argue that the Earth's mass balance of moderately volatile elements is inconsistent with Albarède's hypothesis but is well explained by the standard model of accretion from partially volatile-depleted material, accompanied by core formation.

Modified rare earth semiconductor oxide as a new nucleotide probe.

PubMed

Shrestha, S; Mills, C E; Lewington, J; Tsang, S C

2006-12-28

Recent rapid developments in biological analysis, medical diagnosis, pharmaceutical industry, and environmental control fuel the urgent need for recognition of particular DNA sequences from samples. Currently, DNA detection techniques use radiochemical, enzymatic, fluorescent, or electrochemiluminescent methods; however, these techniques require costly labeled DNA and highly skilled and cumbersome procedure, which prohibit any in-situ monitoring. Here, we report that hybridization of surface-immobilized single-stranded oligonucleotide on praseodymium oxide (evaluated as a biosensor surface for the first time) with complimentary strands in solution provokes a significant shift of electrical impedance curve. This shift is attributed to a change in electrical characteristics through modification of surface charge of the underlying modified praseodymium oxide upon hybridization with the complementary oligonucelotide strand. On the other hand, using a noncomplementary single strand in solution does not create an equivalent change in the impedance value. This result clearly suggests that a new and simple electrochemical technique based on the change in electrical properties of the modified praseodymium oxide semiconductor surface upon recognition and transduction of a biological event without using labeled species is revealed.

Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

PubMed

Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

2014-12-01

In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative stress balance is dysregulated and represents an additional target for treating cholangiocarcinoma.

PubMed

Uchida, Daisuke; Takaki, Akinobu; Ishikawa, Hisashi; Tomono, Yasuko; Kato, Hironari; Tsutsumi, Koichiro; Tamaki, Naofumi; Maruyama, Takayuki; Tomofuji, Takaaki; Tsuzaki, Ryuichiro; Yasunaka, Tetsuya; Koike, Kazuko; Matsushita, Hiroshi; Ikeda, Fusao; Miyake, Yasuhiro; Shiraha, Hidenori; Nouso, Kazuhiro; Yoshida, Ryuichi; Umeda, Yuzo; Shinoura, Susumu; Yagi, Takahito; Fujiwara, Toshiyoshi; Morita, Manabu; Fukushima, Masaki; Yamamoto, Kazuhide; Okada, Hiroyuki

2016-07-01

Pancreatico-biliary malignancies exhibit similar characteristics, including obesity-related features and poor prognosis, and require new treatment strategies. Oxidative stress is known to induce DNA damage and carcinogenesis, and its reduction is viewed as being favorable. However, it also has anti-infection and anti-cancer functions that need to be maintained. To reveal the effect of oxidative stress on cancer progression, we evaluated oxidative stress and anti-oxidative balance in pancreatic cancer (PC) and cholangiocarcinoma (CC) patients, as well as the effect of add-on antioxidant treatment to chemotherapy in a mouse cholangiocarcinoma model. We recruited 84 CC and 80 PC patients who were admitted to our hospital. Serum levels of reactive oxygen metabolites (ROM) and the anti-oxidative OXY-adsorbent test were determined and the balance of these tests was defined as an oxidative index. A diabetic mouse-based cholangiocarcinoma model was utilized to evaluate the effects of add-on antioxidant therapy on cholangiocarcinoma chemotherapy. Serum ROM was higher and anti-oxidant OXY was lower in CC patients with poor outcomes. These parameters were not significantly different in PC patients. In mice, vitamin E administration induced antioxidant hemeoxygenase (HO)-1 protein expression in cancer tissue, while the number of stem-like cells increased. l-carnitine administration improved intestinal microbiome and biliary acid balance, upregulated the hepatic mitochondrial membrane uptake related gene Cpt1 in non-cancerous tissue, and did not alter stem-like cell numbers. Oxidative stress balance was dysregulated in cholangiocarcinoma with poor outcome. The mitochondrial function-supporting agent l-carnitine is a good candidate to control oxidative stress conditions.

Single Additive Enables 3D Printing of Highly Loaded Iron Oxide Suspensions.

PubMed

Hodaei, Amin; Akhlaghi, Omid; Khani, Navid; Aytas, Tunahan; Sezer, Dilek; Tatli, Buse; Menceloglu, Yusuf Z; Koc, Bahattin; Akbulut, Ozge

2018-03-21

A single additive, a grafted copolymer, is designed to ensure the stability of suspensions of highly loaded iron oxide nanoparticles (IOPs) and to facilitate three-dimensional (3D) printing of these suspensions in the filament form. This poly (ethylene glycol)-grafted copolymer of N-[3(dimethylamino)propyl]methacrylamide and acrylic acid harnesses both electrostatic and steric repulsion to realize an optimum formulation for 3D printing. When used at 1.15 wt % (by the weight of IOPs), the suspension attains ∼81 wt % solid loading-96% of the theoretical limit as calculated by the Krieger-Dougherty equation. Rectangular, thick-walled toroidal, and thin-walled toroidal magnetic cores and a porous lattice structure are fabricated to demonstrate the utilization of this suspension as an ink for 3D printing. The electrical and magnetic properties of the magnetic cores are characterized through impedance spectroscopy (IS) and vibrating sample magnetometry (VSM), respectively. The IS indicates the possibility of utilizing wire-wound 3D printed cores as the inductive coils. The VSM verifies that the magnetic properties of IOPs before and after the ink formulation are kept almost unchanged because of the low dosage of the additive. This particle-targeted approach for the formulation of 3D printing inks allows embodiment of a fully aqueous system with utmost target material content.

Characteristics of phase-change materials containing oxide nano-additives for thermal storage.

PubMed

Teng, Tun-Ping; Yu, Chao-Chieh

2012-11-06

In this study, the authors report the production of nanocomposite-enhanced phase-change materials (NEPCMs) using the direct-synthesis method by mixing paraffin with alumina (Al2O3), titania (TiO2), silica (SiO2), and zinc oxide (ZnO) as the experimental samples. Al2O3, TiO2, SiO2, and ZnO were dispersed into three concentrations of 1.0, 2.0, and 3.0 wt.%. Through heat conduction and differential scanning calorimeter experiments to evaluate the effects of varying concentrations of the nano-additives on the heat conduction performance and thermal storage characteristics of NEPCMs, their feasibility for use in thermal storage was determined. The experimental results demonstrate that TiO2 is more effective than the other additives in enhancing both the heat conduction and thermal storage performance of paraffin for most of the experimental parameters. Furthermore, TiO2 reduces the melting onset temperature and increases the solidification onset temperature of paraffin. This allows the phase-change heat to be applicable to a wider temperature range, and the highest decreased ratio of phase-change heat is only 0.46%, compared to that of paraffin. Therefore, this study demonstrates that TiO2, added to paraffin to form NEPCMs, has significant potential for enhancing the thermal storage characteristics of paraffin.

Characteristics of phase-change materials containing oxide nano-additives for thermal storage

PubMed Central

2012-01-01

In this study, the authors report the production of nanocomposite-enhanced phase-change materials (NEPCMs) using the direct-synthesis method by mixing paraffin with alumina (Al2O3), titania (TiO2), silica (SiO2), and zinc oxide (ZnO) as the experimental samples. Al2O3, TiO2, SiO2, and ZnO were dispersed into three concentrations of 1.0, 2.0, and 3.0 wt.%. Through heat conduction and differential scanning calorimeter experiments to evaluate the effects of varying concentrations of the nano-additives on the heat conduction performance and thermal storage characteristics of NEPCMs, their feasibility for use in thermal storage was determined. The experimental results demonstrate that TiO2 is more effective than the other additives in enhancing both the heat conduction and thermal storage performance of paraffin for most of the experimental parameters. Furthermore, TiO2 reduces the melting onset temperature and increases the solidification onset temperature of paraffin. This allows the phase-change heat to be applicable to a wider temperature range, and the highest decreased ratio of phase-change heat is only 0.46%, compared to that of paraffin. Therefore, this study demonstrates that TiO2, added to paraffin to form NEPCMs, has significant potential for enhancing the thermal storage characteristics of paraffin. PMID:23127224

Chemical analysis of extracting transition metal oxides from polymetallic ore by sulphate process

NASA Astrophysics Data System (ADS)

Enkh-Uyanga, Otgon-Uul; Munkhtsetseg, Baatar; Urangoo, Urtnasan; Tserendulam, Enkhtur; Agiimaa, Davaadorj

2017-06-01

In this research work we attempt to improve the purity of polymetallic ores in Mongolia whilst developing practical applications of its refinement processes and this paper presents the results of chemical research of extracting transition metal titanium oxides, ferrous oxide and rare earth oxides from polymetallic ore. Thereby, chemical and mineral analysis of polymetallic ore is carried out basis of responses to the support process at various degrees of water whereas transition metal sulphates solubility differ. As a result of sulphate and resulphurization process we have extracted anatase with 62.5 percent titanium dioxide and brookite mineral with 89.6 percent of titanium dioxide as well as mineral with 83.8 percent of ferrous oxide hematite and rare earth oxides with 57.6 percent of cerium oxide. These oxides are identified under various conditions in the thermal processing. The morphology structure and chemical content compound of the mineral has been verified as a result of the XRF, XRD, SEM-EDX analysis.

Another Earth 2.0? Not So Fast

NASA Astrophysics Data System (ADS)

Schulze-Makuch, Dirk; Guinan, Edward

2016-11-01

The number of confirmed exoplanets now exceeds 3000, with an additional nearly 5000 exoplanet candidates awaiting confirmation in the NASA Exoplanet Archive (2016). Nearly weekly we hear about the detection of a new exoplanet similar in mass to Earth and located in the so-called habitable zone around its host star. The excitement is understandable given our desire to find a second Earth. However, the excitement should not lead to an over-interpretation of the findings, because the claim can only be to have some crude similarity to Earth based on a few selected geophysical parameters. Only a very small fraction of these planets will actually be Earth-like. Earth-like would imply multiple environmental habitats and presence of a sizable biosphere and complex ecosystems, without which Earth, as we experience it, would not exist. Thus, it should be clearly communicated to the public that we are probably still many years away from having the technological capability to detect an Earth-like planet or Earth 2.0 with adequate certainty.

Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

DOE PAGES

Lopez, Kent G.; Cundari, Thomas R.; Gary, J. Brannon

2018-01-17

A computational study of the experimentally proposed mechanism of alkyne diboration by a PDICo complex yielded two fundamental catalytic steps that undergo remarkable electronic changes, PDI = bis(imino)-pyridine. The reactions are envisaged via DFT (density functional theory) and MCSCF (multi-configuration self-consistent field) simulations as (i) a cooperative metal+ligand oxidative addition, and (ii) a sigma-bond metathesis induced ligand-to-metal charge transfer. Analysis of the bonding of pertinent intermediates/TSs also yielded important insight that may be illuminating with regards to the larger field of green catalysis that seeks to ennoble base metals through synergy with potentially redox non-innocent (RNI) ligands. For the presentmore » case, massive changes in electronic structure do not incur massive energetic penalties. Finally, in conjunction with previous research, one may postulate that structural and energetic “fluidity” among several electronic states of RNI-M 3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.« less

Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Kent G.; Cundari, Thomas R.; Gary, J. Brannon

A computational study of the experimentally proposed mechanism of alkyne diboration by a PDICo complex yielded two fundamental catalytic steps that undergo remarkable electronic changes, PDI = bis(imino)-pyridine. The reactions are envisaged via DFT (density functional theory) and MCSCF (multi-configuration self-consistent field) simulations as (i) a cooperative metal+ligand oxidative addition, and (ii) a sigma-bond metathesis induced ligand-to-metal charge transfer. Analysis of the bonding of pertinent intermediates/TSs also yielded important insight that may be illuminating with regards to the larger field of green catalysis that seeks to ennoble base metals through synergy with potentially redox non-innocent (RNI) ligands. For the presentmore » case, massive changes in electronic structure do not incur massive energetic penalties. Finally, in conjunction with previous research, one may postulate that structural and energetic “fluidity” among several electronic states of RNI-M 3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.« less

Iron-carbonate interaction at Earth's core-mantle boundary

NASA Astrophysics Data System (ADS)

Dorfman, S. M.; Badro, J.; Nabiei, F.; Prakapenka, V.; Gillet, P.

2015-12-01

Carbon storage and flux in the deep Earth are moderated by oxygen fugacity and interactions with iron-bearing phases. The amount of carbon stored in Earth's mantle versus the core depends on carbon-iron chemistry at the core-mantle boundary. Oxidized carbonates subducted from Earth's surface to the lowermost mantle may encounter reduced Fe0 metal from disproportionation of Fe2+ in lower mantle silicates or mixing with the core. To understand the fate of carbonates in the lowermost mantle, we have performed experiments on sandwiches of single-crystal (Ca0.6Mg0.4)CO3 dolomite and Fe foil in the laser-heated diamond anvil cell at lower mantle conditions of 49-110 GPa and 1800-2500 K. Syntheses were conducted with in situ synchrotron X-ray diffraction to identify phase assemblages. After quench to ambient conditions, samples were sectioned with a focused Ga+ ion beam for composition analysis with transmission electron microscopy. At the centers of the heated spots, iron melted and reacted completely with the carbonate to form magnesiowüstite, iron carbide, diamond, magnesium-rich carbonate and calcium carbonate. In samples heated at 49 and 64 GPa, the two carbonates exhibit a eutectoid texture. In the sample heated at 110 GPa, the carbonates form rounded ~150-nm-diameter grains with a higher modal proportion of interspersed diamonds. The presence of reduced iron in the deep lower mantle and core-mantle boundary region will promote the formation of diamonds in carbonate-bearing subducted slabs. The complete reaction of metallic iron to oxides and carbides in the presence of mantle carbonate supports the formation of these phases at the Earth's core-mantle boundary and in ultra-low velocity zones.

Some Properties of Beryllium Oxide and Beryllium Oxide - Columbium Ceramals

NASA Technical Reports Server (NTRS)

Robards, C F; Gangler, J J

1951-01-01

High-temperature tensile and thermal-shock investigations were conducted on beryllium oxide and beryllium oxide plus columbium metal additions. X-ray diffraction and metallographic results are given. The tensile strength of 6150 pounds per square inch for beryllium oxide at 1800 degrees F compared favorably with the zirconia bodies previously tested. Additions of 2, 5, 8, 10, 12, and 15 percent by weight of columbium metal failed to improve the shock resistance over that of pure beryllium oxide.

Towards Big Earth Data Analytics: The EarthServer Approach

NASA Astrophysics Data System (ADS)

Baumann, Peter

2013-04-01

import and, hence, duplication); the aforementioned distributed query processing. Additionally, Web clients for multi-dimensional data visualization are being established. Client/server interfaces are strictly based on OGC and W3C standards, in particular the Web Coverage Processing Service (WCPS) which defines a high-level raster query language. We present the EarthServer project with its vision and approaches, relate it to the current state of standardization, and demonstrate it by way of large-scale data centers and their services using rasdaman.

Another Earth 2.0? Not So Fast.

PubMed

Schulze-Makuch, Dirk; Guinan, Edward

2016-11-01

The number of confirmed exoplanets now exceeds 3000, with an additional nearly 5000 exoplanet candidates awaiting confirmation in the NASA Exoplanet Archive ( 2016 ). Nearly weekly we hear about the detection of a new exoplanet similar in mass to Earth and located in the so-called habitable zone around its host star. The excitement is understandable given our desire to find a second Earth. However, the excitement should not lead to an over-interpretation of the findings, because the claim can only be to have some crude similarity to Earth based on a few selected geophysical parameters. Only a very small fraction of these planets will actually be Earth-like. Earth-like would imply multiple environmental habitats and presence of a sizable biosphere and complex ecosystems, without which Earth, as we experience it, would not exist. Thus, it should be clearly communicated to the public that we are probably still many years away from having the technological capability to detect an Earth-like planet or Earth 2.0 with adequate certainty. Key Words: Habitable zone-Second Earth-Habitable planet-Habitability-Life. Astrobiology 16, 817-821.

Scarcity of rare earth elements.

PubMed

de Boer, M A; Lammertsma, K

2013-11-01

Rare earth elements (REEs) are important for green and a large variety of high-tech technologies and are, therefore, in high demand. As a result, supply with REEs is likely to be disrupted (the degree of depends on the REE) in the near future. The 17 REEs are divided into heavy and light REEs. Other critical elements besides REEs, identified by the European Commission, are also becoming less easily available. Although there is no deficiency in the earth's crust of rare earth oxides, the economic accessibility is limited. The increased demand for REEs, the decreasing export from China, and geopolitical concerns on availability contributed to the (re)opening of mines in Australia and the USA and other mines are slow to follow. As a result, short supply of particularly terbium, dysprosium, praseodymium, and neodymium is expected to be problematic for at least the short term, also because they cannot be substituted. Recycling REEs from electronic waste would be a solution, but so far there are hardly any established REE recycling methods. Decreasing the dependency on REEs, for example, by identifying possible replacements or increasing their efficient use, represents another possibility. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Microbial ecology of archaeal ammonia oxidation--a review].

PubMed

Jia, Zhongjun; Weng, Jiahua; Lin, Xiangui; Conrad, Ralf

2010-04-01

Bacteria have long been considered as the key driver of ammonia oxidation on earth. This concept has been challenged recently by the discovery of chemolithoautotrophic isolate of ammonia-oxidizing archaeon in marine. The relative contribution of bacteria and archaea to ammonia oxidation is essential for our understanding of global nitrogen cycle. Recent study suggested a key role of archaeal ammonia oxidation in the marine nitrogen cycle. Our work however revealed the predominace of bacterial ammonia oxidation in agricultural soil. From the biogeochemical perspective, here we summarized the discovery, progress and prospect of archaeal ammonia oxidation. Of great interest in the future would be to elucidate the metabolisms of ammonia-oxidizing archaeon in natural environment and the underlying mechanism that leads to the physiological divergence of ammonia oxidizers.

Rare-Earth-compound nanowires, nanotubes, and fullerene-like nanoparticles: synthesis, characterization, and properties.

PubMed

Wang, Xun; Li, Yadong

2003-11-21

Various low-dimensional nanostructures, such as nanowires, nanotubes, nanosheets, and fullerene-like nanoparticles have been selectively synthesized from rare-earth compounds (hydroxides, fluorides) based on a facile hydrothermal method. The subsequent dehydration, sulfidation, and fluoridation processes lead to the formation of rare-earth oxide, oxysulfide, and oxyhalide nanostructures, which can be functionalized further by doping with other rare-earth ions or by coating with metal nanoparticles. Owing to the interesting combination of novel nanostructures and functional compounds, these nanostructures can be expected to bring new opportunities in the vast research areas of and application in biology, catalysts, and optoelectronic devices.

Prebiotic Chemistry and Atmospheric Warming of Early Earth by an Active Young Sun

NASA Technical Reports Server (NTRS)

Airapetian, V. S.; Glocer, A.; Gronoff, G.; Hebrard, E.; Danchi, W.

2016-01-01

Nitrogen is a critical ingredient of complex biological molecules. Molecular nitrogen, however, which was outgassed Into the Earth's early atmosphere, is relatively chemically inert and nitrogen fixation into more chemically reactive compounds requires high temperatures. Possible mechanisms of nitrogen fixation include lightning, atmospheric shock heating by meteorites, and solar ultraviolet radiation. Here we show that nitrogen fixation in the early terrestrial atmosphere can be explained by frequent and powerful coronal mass ejection events from the young Sun -- so-called superflares. Using magnetohydrodynamic simulations constrained by Kepler Space Telescope observations, we find that successive superflare ejections produce shocks that accelerate energetic particles, which would have compressed the early Earth's magnetosphere. The resulting extended polar cap openings provide pathways for energetic particles to penetrate into the atmosphere and, according to our atmospheric chemistry simulations, initiate reactions converting molecular nitrogen, carbon dioxide and methane to the potent greenhouse gas nitrous oxide as well as hydrogen cyanide, an essential compound for life. Furthermore, the destruction of N2, C02 and CH, suggests that these greenhouse gases cannot explain the stability of liquid water on the early Earth. Instead, we propose that the efficient formation of nitrous oxide could explain a warm early Earth.

Guided earth boring tool

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mc Donald, W.J.; Pittard, G.T.; Maurer, W.C.

A controllable tool for drilling holes in the earth is described comprising a hollow elongated rigid supporting drill pipe having a forward end for entering the earth, means supporting the drill pipe for earth boring or piercing movement, including means for moving the drill pipe longitudinally for penetrating the earth, the drill pipe moving means being constructed to permit addition and removal of supporting drill pipe during earth penetrating operation, a boring mole supported on the forward end of the hollow low drill pipe comprising a cylindrical housing supported on and open to the forward end of the drill pipe,more » a first means on the front end for applying a boring force to the soil comprising an anvil having a striking surface inside the housing and a boring surface outside the housing, a second means comprising a reciprocally movable hammer positioned in the housing to apply a percussive force to the anvil striking surface for transmitting a percussive force to the boring force applying means, and means permitting introduction of air pressure supplied through the hollow pipe into the housing for operating the hammer and for discharging spent air from the housing to the hole being bored, and the tool being operable to penetrate the earth upon longitudinal movement of the drill rod by the longitudinal rod moving means and operation of the mole by reciprocal movement of the hammer.« less

Ferric Iron Production in Magma Oceans and Evolution of Mantle Oxidation State

NASA Astrophysics Data System (ADS)

Schaefer, L.; Elkins-Tanton, L. T.; Pahlevan, K.

2018-05-01

Self-oxidation of the magma ocean by ferric iron production at high pressure may explain the mantle oxidation state of the Earth. Partitioning during fractional crystallization can further increase the mantle oxygen fugacity during solidification.

Protective effect of rare earth against oxidative stress under ultraviolet-B radiation.

PubMed

Wang, Lihong; Huang, Xiaohua; Zhou, Qing

2009-04-01

The effects of lanthanum (III) (La(III)) in protecting soybean leaves against oxidative stress induced by ultraviolet-B (UV-B) radiation were investigated. The increase in contents of hydrogen peroxide (H(2)O(2)) and superoxide (O2*-) due to UV-B radiation suggested oxidative stress. The increase in the content of malondialdehyde (MDA) and the decrease in the index of unsaturated fatty acid (IUFA) indicated oxidative damage on cell membrane induced by UV-B radiation. La(III) partially reversed UV-B-radiation-induced damage of plant growth. The reduction in the contents of H(2)O(2), O2*-, and MDA and increase in the content of IUFA, compared with UV-B treatment, also indicated that La(III) alleviated the oxidative damage induced by UV-B radiation. The increase in the activities of superoxide dismutase and peroxidase and the contents of ascorbate, carotenoids, and flavonoids were observed in soybean leaves with La(III) + UV-B treatment, compared with UV-B treatment. Our data suggested that La(III) could protect soybean plants from UV-B-radiation-induced oxidative stress by reacting with reactive oxygen species directly or by improving the defense system of plants.

Investigation of the Effect of Various Oxide and Fluoride Additives on the Microstructure, Electronic Properties, and Phase Shifting Ability of Ba(1-x) Sr(x)TiO3

DTIC Science & Technology

1993-09-01

AD-A271 756 ARMY RESEARCH LABORATORY Investigation of the Effect of Various Oxide and Flouride Additives on the Microstructure, Electronic Properties ...NUMBERS Investigation of the Effect of Various Oxide and Fluoride Additives on the Microstructure, Electronic Properties , and Phase Shifting Ability of...dielectric properties . tunability. hysteresis. and grain size have been investigated. The homogeneity of the doped materials has been verified using

Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

PubMed

Garg, Shikha; Wang, Kai; Waite, T David

2017-05-16

Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

Grid Computing for Earth Science

NASA Astrophysics Data System (ADS)

Renard, Philippe; Badoux, Vincent; Petitdidier, Monique; Cossu, Roberto

2009-04-01

The fundamental challenges facing humankind at the beginning of the 21st century require an effective response to the massive changes that are putting increasing pressure on the environment and society. The worldwide Earth science community, with its mosaic of disciplines and players (academia, industry, national surveys, international organizations, and so forth), provides a scientific basis for addressing issues such as the development of new energy resources; a secure water supply; safe storage of nuclear waste; the analysis, modeling, and mitigation of climate changes; and the assessment of natural and industrial risks. In addition, the Earth science community provides short- and medium-term prediction of weather and natural hazards in real time, and model simulations of a host of phenomena relating to the Earth and its space environment. These capabilities require that the Earth science community utilize, both in real and remote time, massive amounts of data, which are usually distributed among many different organizations and data centers.

Energetics and Defect Interactions of Complex Oxides for Energy Applications

NASA Astrophysics Data System (ADS)

Solomon, Jonathan Michael

energetic stability for La solid solutions than for Y. Additionally, calculations performed for different atomic configurations show a preference for reduced (increased) oxygen vacancy coordination around La (Y) dopants. The current results are shown to be qualitatively consistent with related calculations and calorimetric measurements of heats of formation in other trivalent doped fluorite oxides, which show a tendency for increasing stability and increasing preference for higher oxygen coordination with increasing size of the trivalent impurity. We expand this investigation by considering a series of trivalent rare earth fission product cations, specifically, Y3+ (1.02 A, Shannon radius with eightfold coordination), Dy3+ (1.03 A), Gd 3+ (1.05 A), Eu3+ (1.07 A), Sm3+ (1.08 A), Pm3+ (1.09 A), Nd3+ (1.11 A), Pr3+ (1.13 A), Ce3+ (1.14 A) and La3+ (1.16 A). Compounds with ionic radius of the M3+ species smaller or larger than 1.09 A are found to have energetically preferred defect ordering arrangements. Systems with preferred defect ordering arrangements are suggestive of defect clustering in short range ordered solid solutions, which is expected to limit oxygen ion mobility and therefore the rate of oxidation of spent nuclear fuel. Finally, the energetics of rare earth substituted (M3+= La, Y, and Nd) UO2 solid solutions are investigated by employing a combination of calorimetric measurements and DFT based computations. The calorimetric studies are performed by Lei Zhang and Professor Alexandra Navrotsky at the University of Calfornia, Davis, as part of a joint computational/ experimental collaborative effort supported through the Materials Science of Actinides Energy Frontier Research Center. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are

Biological modulation of planetary atmospheres: The early Earth scenario

NASA Technical Reports Server (NTRS)

Schidlowski, M.

1985-01-01

The establishment and subsequent evolution of life on Earth had a profound impact on the chemical regime at the planet's surface and its atmosphere. A thermodynamic gradient was imposed on near-surface environments that served as the driving force for a number on important geochemical transformations. An example is the redox imbalance between the modern atmosphere and the material of the Earth's crust. Current photochemical models predict extremely low partial pressures of oxygen in the Earth's prebiological atmosphere. There is widespread consensus that any large-scale oxygenation of the primitive atmosphere was contingent on the advent of biological (autotrophic) carbon fixation. It is suggested that photoautotrophy existed both as a biochemical process and as a geochemical agent since at least 3.8 Ga ago. Combining the stoichiometry of the photosynthesis reaction with a carbon isotope mass balance and current concepts for the evolution of the stationary sedimentary mass as a funion of time, it is possible to quantify, the accumulation of oxygen and its photosynthetic oxidation equivalents through Earth history.

Google Earth Engine

NASA Astrophysics Data System (ADS)

Gorelick, Noel

2013-04-01

The Google Earth Engine platform is a system designed to enable petabyte-scale, scientific analysis and visualization of geospatial datasets. Earth Engine provides a consolidated environment including a massive data catalog co-located with thousands of computers for analysis. The user-friendly front-end provides a workbench environment to allow interactive data and algorithm development and exploration and provides a convenient mechanism for scientists to share data, visualizations and analytic algorithms via URLs. The Earth Engine data catalog contains a wide variety of popular, curated datasets, including the world's largest online collection of Landsat scenes (> 2.0M), numerous MODIS collections, and many vector-based data sets. The platform provides a uniform access mechanism to a variety of data types, independent of their bands, projection, bit-depth, resolution, etc..., facilitating easy multi-sensor analysis. Additionally, a user is able to add and curate their own data and collections. Using a just-in-time, distributed computation model, Earth Engine can rapidly process enormous quantities of geo-spatial data. All computation is performed lazily; nothing is computed until it's required either for output or as input to another step. This model allows real-time feedback and preview during algorithm development, supporting a rapid algorithm development, test, and improvement cycle that scales seamlessly to large-scale production data processing. Through integration with a variety of other services, Earth Engine is able to bring to bear considerable analytic and technical firepower in a transparent fashion, including: AI-based classification via integration with Google's machine learning infrastructure, publishing and distribution at Google scale through integration with the Google Maps API, Maps Engine and Google Earth, and support for in-the-field activities such as validation, ground-truthing, crowd-sourcing and citizen science though the Android Open Data

Google Earth Engine

NASA Astrophysics Data System (ADS)

Gorelick, N.

2012-12-01

The Google Earth Engine platform is a system designed to enable petabyte-scale, scientific analysis and visualization of geospatial datasets. Earth Engine provides a consolidated environment including a massive data catalog co-located with thousands of computers for analysis. The user-friendly front-end provides a workbench environment to allow interactive data and algorithm development and exploration and provides a convenient mechanism for scientists to share data, visualizations and analytic algorithms via URLs. The Earth Engine data catalog contains a wide variety of popular, curated datasets, including the world's largest online collection of Landsat scenes (> 2.0M), numerous MODIS collections, and many vector-based data sets. The platform provides a uniform access mechanism to a variety of data types, independent of their bands, projection, bit-depth, resolution, etc..., facilitating easy multi-sensor analysis. Additionally, a user is able to add and curate their own data and collections. Using a just-in-time, distributed computation model, Earth Engine can rapidly process enormous quantities of geo-spatial data. All computation is performed lazily; nothing is computed until it's required either for output or as input to another step. This model allows real-time feedback and preview during algorithm development, supporting a rapid algorithm development, test, and improvement cycle that scales seamlessly to large-scale production data processing. Through integration with a variety of other services, Earth Engine is able to bring to bear considerable analytic and technical firepower in a transparent fashion, including: AI-based classification via integration with Google's machine learning infrastructure, publishing and distribution at Google scale through integration with the Google Maps API, Maps Engine and Google Earth, and support for in-the-field activities such as validation, ground-truthing, crowd-sourcing and citizen science though the Android Open Data

The Sun: Source of the Earth's Energy

NASA Technical Reports Server (NTRS)

Thompson, Barbara J.; Fisher, Richard R. (Technical Monitor)

2001-01-01

The Sun is the primary source of the Earth's energy. However, due to the complexity in the way the energy affects Earth, the various solar sources of the energy, and the variation exhibited by the Sun it is difficult to understand and predict the Earth's response to solar drivers. In addition to visible light the radiant energy of the Sun can exhibit variation in nearly all wavelengths, which can vary over nearly all timescales. Depending on the wavelength of the incident radiation the light can deposit energy in a wide variety or locations and drive processes from below Earth's surface to interplanetary space. Other sources of energy impacting Earth include energetic particles, magnetic fields, and mass and flow variations in the solar wind. Many of these variable energetic processes cannot be coupled and recent results continue to demonstrate that the complex dynamics of the Sun can have a great range of measurable impacts on Earth.

Additional consumption of one egg per day increases serum lutein plus zeaxanthin concentration and lowers oxidized low-density lipoprotein in moderately hypercholesterolemic males.

PubMed

Kishimoto, Yoshimi; Taguchi, Chie; Saita, Emi; Suzuki-Sugihara, Norie; Nishiyama, Hiroshi; Wang, Wei; Masuda, Yasunobu; Kondo, Kazuo

2017-09-01

The egg is a nutrient-dense food and contains antioxidative carotenoids, lutein and zeaxanthin, but its impact on serum cholesterol levels has been a matter of concern, especially for individuals who have high serum cholesterol levels. We conducted this study to determine whether and how the daily additional consumption of one egg affects serum lipid profiles and parameters of LDL oxidation in moderately hypercholesterolemic males. Nineteen male Japanese adults (total cholesterol [TC]>5.2mmol/L) participated, consuming one soft boiled egg per day for 4weeks in addition to their habitual diet. Despite the significant increase in their intake of dietary cholesterol during the intervention period, the subjects' serum concentrations of TC and low-density lipoprotein cholesterol (LDL-C) did not increase. Their serum malondialdehyde modified low-density lipoprotein (MDA-LDL) concentrations were significantly decreased and their LDL oxidation lag times, reflecting the resistance of free-radical-induced LDL lipid peroxidation (ex vivo), was prolonged after 2 and 4weeks. At weeks 2 and 4, the subjects' serum lutein+zeaxanthin concentrations were significantly higher than their baseline values and showed both an inverse relation with MDA-LDL and a positive relationship with the LDL oxidation lag time. These data showed that in moderately hypercholesterolemic males, the additional consumption of one egg per day for 4weeks did not have adverse effects on serum TC or LDL-C, and it might reduce the susceptibility of LDL to oxidation through an increase in the serum lutein and zeaxanthin concentrations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molybdenum-based additives to mixed-metal oxides for use in hot gas cleanup sorbents for the catalytic decomposition of ammonia in coal gases

DOEpatents

Ayala, Raul E.

1993-01-01

This invention relates to additives to mixed-metal oxides that act simultaneously as sorbents and catalysts in cleanup systems for hot coal gases. Such additives of this type, generally, act as a sorbent to remove sulfur from the coal gases while substantially simultaneously, catalytically decomposing appreciable amounts of ammonia from the coal gases.

Rare earth element geochemistry of feldspars: examples from Fe-oxide Cu-Au systems in the Olympic Cu-Au Province, South Australia

NASA Astrophysics Data System (ADS)

Kontonikas-Charos, Alkis; Ciobanu, Cristiana L.; Cook, Nigel J.; Ehrig, Kathy; Krneta, Sasha; Kamenetsky, Vadim S.

2018-04-01

Rare earth element (REE) fractionation trends in feldspars are reported from Olympic Dam (including Wirrda Well and Phillip's Ridge) and Cape Donington (Port Lincoln), for comparison with two other igneous-hydrothermal terranes within the eastern Gawler Craton: Moonta-Wallaroo and Hillside. The case studies were selected as they represent 1590 Ma Hiltaba Suite and/or 1845 - 1810 Ma Donington Suite granites, and, aside from Cape Donington, are associated with Mesoproterozoic iron-oxide copper gold (IOCG)-type mineralization. Both plagioclase and alkali feldspar were analyzed within selected samples with the purpose of constraining and linking changes in REE concentrations and fractionation trends in feldspars to local and whole-rock textures and geochemistry. Two unique, reproducible fractionation trends were obtained for igneous plagioclase and alkali feldspars, distinguished from one another by light rare earth element enrichment, Eu-anomalies and degrees of fractionation (e.g. La/Lu slopes). Results for hydrothermal albite and K-feldspar indicate that REE concentrations and fractionation trends are generally inherited from igneous predecessors, however in some instances, significant amounts of REE appear to have been lost to the fluid. These results may have critical implications for the formation of world-class IOCG systems, in which widespread alkali metasomatism plays a key role by altering the physical and chemical properties of the host rocks during early stages of IOCG formation, as well as trapping trace elements (including REE).

Replacing the Rare Earth Intellectual Capital

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gschneidner, Jr., Karl

2011-04-01

The rare earth crisis slowly evolved during a 10 to 15 year period beginning in the mid-1980s, when the Chinese began to export mixed rare earth concentrates. In the early 1990s, they started to move up the supply chain and began to export the individual rare earth oxides and metals. By the late 1990s the Chinese exported higher value products, such as magnets, phosphors, polishing compounds, catalysts; and in the 21st century they supplied finished products including electric motors, computers, batteries, liquid-crystal displays (LCDs), TVs and monitors, mobile phones, iPods and compact fluorescent lamp (CFL) light bulbs. As they movedmore » to higher value products, the Chinese slowly drove the various industrial producers and commercial enterprises in the US, Europe and Japan out of business by manipulating the rare earth commodity prices. Because of this, the technically trained rare earth engineers and scientists who worked in areas from mining to separations, to processing to production, to manufacturing of semifinished and final products, were laid-off and moved to other fields or they retired. However, in the past year the Chinese have changed their philosophy of the 1970s and 1980s of forming a rare earth cartel to control the rare earth markets to one in which they will no longer supply the rest of the world (ROW) with their precious rare earths, but instead will use them internally to meet the growing demand as the Chinese standard of living increases. To this end, they have implemented and occasionally increased export restrictions and added an export tariff on many of the high demand rare earth elements. Now the ROW is quickly trying to start up rare earth mines, e.g. Molycorp Minerals in the US and Lynas Corp. in Australia, to cover this shortfall in the worldwide market, but it will take about five years for the supply to meet the demand, even as other mines in the ROW become productive. Unfortunately, today there is a serious lack of technically

Biological consilience of hydrogen sulfide and nitric oxide in plants: Gases of primordial earth linking plant, microbial and animal physiologies.

PubMed

Yamasaki, Hideo; Cohen, Michael F

2016-05-01

Hydrogen sulfide (H2S) is produced in the mammalian body through the enzymatic activities of cystathionine β-synthase (CBS), cystathionine γ-lyase (CSE) and 3-mercaptopyruvate sulfurtransferase (3MST). A growing number of studies have revealed that biogenic H2S produced in tissues is involved in a variety of physiological responses in mammals including vasorelaxation and neurotransmission. It is now evident that mammals utilize H2S to regulate multiple signaling systems, echoing the research history of the gaseous signaling molecules nitric oxide (NO) and carbon monoxide (CO) that had previously only been recognized for their cytotoxicity. In the human diet, meats (mammals, birds and fishes) and vegetables (plants) containing cysteine and other sulfur compounds are the major dietary sources for endogenous production of H2S. Plants are primary producers in ecosystems on the earth and they synthesize organic sulfur compounds through the activity of sulfur assimilation. Although plant H2S-producing activities have been known for a long time, our knowledge of H2S biology in plant systems has not been updated to the extent of mammalian studies. Here we review recent progress on H2S studies, highlighting plants and bacteria. Scoping the future integration of H2S, NO and O2 biology, we discuss a possible linkage between physiology, ecology and evolutional biology of gas metabolisms that may reflect the historical changes of the Earth's atmospheric composition. Copyright © 2016 Elsevier Inc. All rights reserved.

Chemical bonding analysis on amphoteric hydrogen - alkaline earth ammine borohydrides

NASA Astrophysics Data System (ADS)

Kiruthika, S.; Ravindran, P.

2018-04-01

Usually the ions in solid are in the positive oxidation states or in the negative oxidation state depending upon the chemical environment. It is highly unusual for an ion having both positive as well as negative oxidation state in a particular compound. Structural analysis suggest that the alkaline earth ammine borohydrides (AABH) with the chemical formula M (BH4)2(NH3)2 (M = Mg, Ca, or Sr) where hydrogen is present in +1 and -1 oxidation states. In order to understand the oxidation states of hydrogen and also the character of chemical bond present in AABH we have made charge density, electron localization function, Born effective charge, Bader effective charge, and density of states analyses using result from the density functional calculations. Our detailed analyses show that hydrogen is in amphoteric behavior with hydrogen closer to boron is in negative oxidation state and that closer to nitrogen is in the positive oxidation state. Due to the presence of finite covalent bonding between the consitutents in AABH the oxidation state of hydrogen is non-interger value. The confirmation of the presence of amphtoric behavior of hydrogen in AABH has implication in hydrogen storage applications.

Use of thulium-sensitized rare earth-doped low phonon energy crystalline hosts for IR sources.

PubMed

Ganem, Joseph; Bowman, Steven R

2013-11-01

Crystalline hosts with low phonon energies enable novel energy transfer processes when doped with rare earth ions. Two applications of energy transfer for rare earth ions in thulium-sensitized low phonon energy crystals that result in infrared luminescence are discussed. One application is an endothermic, phonon-assisted cross-relaxation process in thulium-doped yttrium chloride that converts lattice phonons to infrared emission, which raises the possibility of a fundamentally new method for achieving solid-state optical cooling. The other application is an optically pumped mid-IR phosphor using thulium-praseodymium-doped potassium lead chloride that converts 805-nm diode light to broadband emission from 4,000 to 5,500 nm. These two applications in chloride crystals are discussed in terms of critical radii calculated from Forster-Dexter energy transfer theory. It is found that the critical radii for electric dipole-dipole interactions in low phonon energy chloride crystals are comparable to those in conventional oxide and fluoride crystals. It is the reduction in multi-phonon relaxation rates in chloride crystals that enable these additional energy transfer processes and infrared luminescence.

Use of thulium-sensitized rare earth-doped low phonon energy crystalline hosts for IR sources

PubMed Central

2013-01-01

Crystalline hosts with low phonon energies enable novel energy transfer processes when doped with rare earth ions. Two applications of energy transfer for rare earth ions in thulium-sensitized low phonon energy crystals that result in infrared luminescence are discussed. One application is an endothermic, phonon-assisted cross-relaxation process in thulium-doped yttrium chloride that converts lattice phonons to infrared emission, which raises the possibility of a fundamentally new method for achieving solid-state optical cooling. The other application is an optically pumped mid-IR phosphor using thulium-praseodymium-doped potassium lead chloride that converts 805-nm diode light to broadband emission from 4,000 to 5,500 nm. These two applications in chloride crystals are discussed in terms of critical radii calculated from Forster-Dexter energy transfer theory. It is found that the critical radii for electric dipole-dipole interactions in low phonon energy chloride crystals are comparable to those in conventional oxide and fluoride crystals. It is the reduction in multi-phonon relaxation rates in chloride crystals that enable these additional energy transfer processes and infrared luminescence. PMID:24180684

Use of thulium-sensitized rare earth-doped low phonon energy crystalline hosts for IR sources

NASA Astrophysics Data System (ADS)

Ganem, Joseph; Bowman, Steven R.

2013-11-01

Crystalline hosts with low phonon energies enable novel energy transfer processes when doped with rare earth ions. Two applications of energy transfer for rare earth ions in thulium-sensitized low phonon energy crystals that result in infrared luminescence are discussed. One application is an endothermic, phonon-assisted cross-relaxation process in thulium-doped yttrium chloride that converts lattice phonons to infrared emission, which raises the possibility of a fundamentally new method for achieving solid-state optical cooling. The other application is an optically pumped mid-IR phosphor using thulium-praseodymium-doped potassium lead chloride that converts 805-nm diode light to broadband emission from 4,000 to 5,500 nm. These two applications in chloride crystals are discussed in terms of critical radii calculated from Forster-Dexter energy transfer theory. It is found that the critical radii for electric dipole-dipole interactions in low phonon energy chloride crystals are comparable to those in conventional oxide and fluoride crystals. It is the reduction in multi-phonon relaxation rates in chloride crystals that enable these additional energy transfer processes and infrared luminescence.

A combined toxicity study of zinc oxide nanoparticles and vitamin C in food additives

NASA Astrophysics Data System (ADS)

Wang, Yanli; Yuan, Lulu; Yao, Chenjie; Ding, Lin; Li, Chenchen; Fang, Jie; Sui, Keke; Liu, Yuanfang; Wu, Minghong

2014-11-01

At present, safety evaluation standards for nanofood additives are made based on the toxic effects of a single additive. Since the size, surface properties and chemical nature influence the toxicity of nanomaterials, the toxicity may have dramatically changed when nanomaterials are used as food additives in a complex system. Herein, we investigated the combined toxicity of zinc oxide nanoparticles (ZnO NPs) and vitamin C (Vc, ascorbic acid). The results showed that Vc increased the cytotoxicity significantly compared with that of the ZnO only NPs. When the cells were exposed to ZnO NPs at a concentration less than 15 mg L-1, or to Vc at a concentration less than 300 mg L-1, there was no significant cytotoxicity, both in the case of gastric epithelial cell line (GES-1) and neural stem cells (NSCs). However, when 15 mg L-1 of ZnO NPs and 300 mg L-1 of Vc were introduced to cells together, the cell viability decreased sharply indicating significant cytotoxicity. Moreover, the significant increase in toxicity was also shown in the in vivo experiments. The dose of the ZnO NPs and Vc used in the in vivo study was calculated according to the state of food and nutrition enhancer standard. After repeated oral exposure to ZnO NPs plus Vc, the injury of the liver and kidneys in mice has been indicated by the change of these indices. These findings demonstrate that the synergistic toxicity presented in a complex system is essential for the toxicological evaluation and safety assessment of nanofood.At present, safety evaluation standards for nanofood additives are made based on the toxic effects of a single additive. Since the size, surface properties and chemical nature influence the toxicity of nanomaterials, the toxicity may have dramatically changed when nanomaterials are used as food additives in a complex system. Herein, we investigated the combined toxicity of zinc oxide nanoparticles (ZnO NPs) and vitamin C (Vc, ascorbic acid). The results showed that Vc increased the

EarthLabs: A National Model for Earth Science Lab Courses

NASA Astrophysics Data System (ADS)

McDaris, J. R.; Dahlman, L.; Barstow, D.

2008-12-01

As a response to the need for more rigorous, inquiry-based high school Earth science courses, a coalition of scientists, educators, and five states have created EarthLabs, a set of pilot modules that can serve as a national model for lab-based science courses. The content of EarthLabs chapters focuses on Earth system science and environmental literacy and conforms to the National Science Education Standards as well as the states' curriculum frameworks. The effort is funded by NOAA's Environmental Literacy program. The pilot modules present activities on Corals, Drought, Fisheries, and Hurricanes. The Fisheries and Hurricanes units were reviewed and field-tested by educators in Texas and Arizona. The feedback from this evaluation led to revisions of these units and guided development of the Corals and Drought chapters. Each module consists of activities that use online data sets, satellite imagery, web-based readings, and hands-on laboratory experiments. The project comprises two separate websites, one for the instructor and one for students. The instructor's site contains the pedagogical underpinnings for each lab including teaching materials, assessment strategies, and the alignment of activities with state and national science standards. The student site provides access to all materials that students need to complete the activities or, in the case of the hands-on labs, where they access additional information to help extend their learning. There are also formative and summative questions embedded in the student webpages to help scaffold learning through the activities.

Moving Closer to EarthScope: A Major New Initiative for the Earth Sciences*

NASA Astrophysics Data System (ADS)

Simpson, D.; Blewitt, G.; Ekstrom, G.; Henyey, T.; Hickman, S.; Prescott, W.; Zoback, M.

2002-12-01

EarthScope is a scientific research and infrastructure initiative designed to provide a suite of new observational facilities to address fundamental questions about the evolution of continents and the processes responsible for earthquakes and volcanic eruptions. The integrated observing systems that will comprise EarthScope capitalize on recent developments in sensor technology and communications to provide Earth scientists with synoptic and high-resolution data derived from a variety of geophysical sensors. An array of 400 broadband seismometers will spend more than ten years crossing the contiguous 48 states and Alaska to image features that make up the internal structure of the continent and underlying mantle. Additional seismic and electromagnetic instrumentation will be available for high resolution imaging of geological targets of special interest. A network of continuously recording Global Positioning System (GPS) receivers and sensitive borehole strainmeters will be installed along the western U.S. plate boundary. These sensors will measure how western North America is deforming, what motions occur along faults, how earthquakes start, and how magma flows beneath active volcanoes. A four-kilometer deep observatory bored directly into the San Andreas fault will provide the first opportunity to observe directly the conditions under which earthquakes occur, to collect fault rocks and fluids for laboratory study, and to monitor continuously an active fault zone at depth. All data from the EarthScope facilities will be openly available in real-time to maximize participation from the scientific community and to provide on-going educational outreach to students and the public. EarthScope's sensors will revolutionize observational Earth science in terms of the quantity, quality and spatial extent of the data they provide. Turning these data into exciting scientific discovery will require new modes of experimentation and interdisciplinary cooperation from the Earth

Effect of herbal feed additives on performance parameters, intestinal microbiota, intestinal morphology and meat lipid oxidation of broiler chickens.

PubMed

Giannenas, Ilias; Bonos, Eleftherios; Skoufos, Ioannis; Tzora, Athina; Stylianaki, Ioanna; Lazari, Diamanto; Tsinas, Anastasios; Christaki, Efterpi; Florou-Paneri, Panagiota

2018-06-06

1. This feeding trial investigated the effects of herbal feed additives on performance of broiler chickens, jejunal and caecal microbiota, jejunal morphology, and meat chemical composition and oxidative stability during refrigerated storage. 2. In a 42 days trial, 320 one-day-old broiler chickens were randomly allocated to four groups with four replicate pens each containing 20 chicks. The control group was fed maize-soybean-based diets. The diets of the other three groups were supplemented with herbal feed additives: HRB1 with Stresomix TM (0.5 g/kg feed); HRB2 with Ayucee TM (1.0 g/kg feed); HRB3 with Salcochek Pro TM (1.0 g/kg feed). The GC/MS analysis of the feed additives showed that the major components of HRB1 were β-caryophyllene (14.4%) and menthol (9.8%); HRB2 were n-hexadecanoic acid (14.22%) and β-caryophyllene (14.4%) and HRB3 were menthol (69.6%) and clavicol methyl ether (13.9%). 3. Intestinal samples were taken at 42 d to determine bacterial populations (total aerobe counts, Lactobacilli, and Escherichia coli) and perform gut morphology analysis. Meat samples were analysed for chemical composition and oxidative stability under storage. 4. The HRB1 group had improved (P<0.05) body weight gain and tended to have improved (0.05≤P<0.10) feed conversion ratio, compared to the control group. Jejunum lactic acid bacteria counts were increased (P<0.001) in groups HRB1 and HRB3, compared to the control group, whereas caecal lactic acid bacteria counts tended to increase (0.05≤ P< 0.10) in group HRB1, compared to the control group. Breast meat fat content tended to be lower (0.05≤ P< 0.10) in group HRB1. Meat oxidative stability was improved (P<0.001) and jejunum villus height, crypt depth and goblet cells numbers were increased (P<0.001) in all three herbal supplemented groups, compared to the control. 5. In conclusion, herbal feed additives may be able to improve both growth performance and antioxidant activity of broiler chickens, based on their

World Wind 3D Earth Viewing

NASA Technical Reports Server (NTRS)

Hogan, Patrick; Maxwell, Christopher; Kim, Randolph; Gaskins, Tom

2007-01-01

World Wind allows users to zoom from satellite altitude down to any place on Earth, leveraging high-resolution LandSat imagery and SRTM (Shuttle Radar Topography Mission) elevation data to experience Earth in visually rich 3D. In addition to Earth, World Wind can also visualize other planets, and there are already comprehensive data sets for Mars and the Earth's moon, which are as easily accessible as those of Earth. There have been more than 20 million downloads to date, and the software is being used heavily by the Department of Defense due to the code s ability to be extended and the evolution of the code courtesy of NASA and the user community. Primary features include the dynamic access to public domain imagery and its ease of use. All one needs to control World Wind is a two-button mouse. Additional guides and features can be accessed through a simplified menu. A JAVA version will be available soon. Navigation is automated with single clicks of a mouse, or by typing in any location to automatically zoom in to see it. The World Wind install package contains the necessary requirements such as the .NET runtime and managed DirectX library. World Wind can display combinations of data from a variety of sources, including Blue Marble, LandSat 7, SRTM, NASA Scientific Visualization Studio, GLOBE, and much more. A thorough list of features, the user manual, a key chart, and screen shots are available at http://worldwind.arc.nasa.gov.

Using EarthLabs to Enhance Earth Science Curriculum in Texas

NASA Astrophysics Data System (ADS)

Chegwidden, D. M.; Ellins, K. K.; Haddad, N.; Ledley, T. S.

2012-12-01

As an educator in Texas, a state that values and supports an Earth Science curriculum, I find it essential to educate my students who are our future voting citizens and tax payers. It is important to equip them with tools to understand and solve the challenges of solving of climate change. As informed citizens, students can help to educate others in the community with basic knowledge of weather and climate. They can also help to dispose of the many misconceptions that surround the climate change, which is perceived as a controversial topic. As a participant in a NSF-sponsored Texas Earth and Space (TXESS) Revolution teacher professional development program, I was selected to participate in a curriculum development project led by TERC to develop and test education resources for the EarthLabs climate literacy collection. I am involved in the multiple phases of the project, including reviewing labs that comprise the Climate, Weather and Biosphere module during the development phase, pilot teaching the module with my students, participating in research, and delivering professional development to other Texas teachers to expose them to the content found in the module and to encourage them to incorporate it into their teaching. The Climate, Weather and the Biosphere module emphasizes different forms of evidence and requires that learners apply different inquiry-based approaches to build the knowledge they need to develop as climate literate citizens. My involvement with the EarthLabs project has strengthened my overall knowledge and confidence to teach about Earth's climate system and climate change. In addition, the project has produced vigorous classroom discussion among my students as well as encouraged me to collaborate with other educators through our delivery of professional development to other teachers. In my poster, I will share my experiences, describe the impact the curriculum has made on my students, and report on challenges and valuable lessons gained by

Benefits of neutral electrolyzed oxidizing water as a drinking water additive for broiler chickens.

PubMed

Bügener, E; Kump, A Wilms-Schulze; Casteel, M; Klein, G

2014-09-01

In the wake of discussion about the use of drugs in food-producing farms, it seems to be more and more important to search for alternatives and supportive measures to improve health. In this field trial, the influence of electrolyzed oxidizing (EO) water on water quality, drug consumption, mortality, and performance parameters such as BW and feed conversion rate was investigated on 2 broiler farms. At each farm, 3 rearing periods were included in the study. With EO water as the water additive, the total viable cell count and the number of Escherichia coli in drinking water samples were reduced compared with the respective control group. The frequency of treatment days was represented by the number of used daily doses per population and showed lower values in EO-water-treated groups at both farms. Furthermore, the addition of EO water resulted in a lower mortality rate. In terms of analyzed performance parameters, no significant differences were determined. In this study, the use of EO water improved drinking water quality and seemed to reduce the drug use without showing negative effects on performance parameters and mortality rates. © 2014 Poultry Science Association Inc.

Electrons, life and the evolution of Earth's oxygen cycle.

PubMed

Falkowski, Paul G; Godfrey, Linda V

2008-08-27

The biogeochemical cycles of H, C, N, O and S are coupled via biologically catalysed electron transfer (redox) reactions. The metabolic processes responsible for maintaining these cycles evolved over the first ca 2.3 Ga of Earth's history in prokaryotes and, through a sequence of events, led to the production of oxygen via the photobiologically catalysed oxidation of water. However, geochemical evidence suggests that there was a delay of several hundred million years before oxygen accumulated in Earth's atmosphere related to changes in the burial efficiency of organic matter and fundamental alterations in the nitrogen cycle. In the latter case, the presence of free molecular oxygen allowed ammonium to be oxidized to nitrate and subsequently denitrified. The interaction between the oxygen and nitrogen cycles in particular led to a negative feedback, in which increased production of oxygen led to decreased fixed inorganic nitrogen in the oceans. This feedback, which is supported by isotopic analyses of fixed nitrogen in sedimentary rocks from the Late Archaean, continues to the present. However, once sufficient oxygen accumulated in Earth's atmosphere to allow nitrification to out-compete denitrification, a new stable electron 'market' emerged in which oxygenic photosynthesis and aerobic respiration ultimately spread via endosymbiotic events and massive lateral gene transfer to eukaryotic host cells, allowing the evolution of complex (i.e. animal) life forms. The resulting network of electron transfers led a gas composition of Earth's atmosphere that is far from thermodynamic equilibrium (i.e. it is an emergent property), yet is relatively stable on geological time scales. The early coevolution of the C, N and O cycles, and the resulting non-equilibrium gaseous by-products can be used as a guide to search for the presence of life on terrestrial planets outside of our Solar System.

Strategy for earth explorers in global earth sciences

NASA Technical Reports Server (NTRS)

1988-01-01

The goal of the current NASA Earth System Science initiative is to obtain a comprehensive scientific understanding of the Earth as an integrated, dynamic system. The centerpiece of the Earth System Science initiative will be a set of instruments carried on polar orbiting platforms under the Earth Observing System program. An Earth Explorer program can open new vistas in the earth sciences, encourage innovation, and solve critical scientific problems. Specific missions must be rigorously shaped by the demands and opportunities of high quality science and must complement the Earth Observing System and the Mission to Planet Earth. The committee believes that the proposed Earth Explorer program provides a substantial opportunity for progress in the earth sciences, both through independent missions and through missions designed to complement the large scale platforms and international research programs that represent important national commitments. The strategy presented is intended to help ensure the success of the Earth Explorer program as a vital stimulant to the study of the planet.

Radar Discovery and Characterization of Binary Near-Earth Asteroids

NASA Technical Reports Server (NTRS)

Margot, J. L.; Nolan, M. C.; Benner, L. A. M.; Ostro, S. J.; Jurgens, R. F.; Giorgini, J. D.; Slade, M. A.; Howell, E. S.; Campbell, D. B.

2002-01-01

The radar instruments at Arecibo and Goldstone recently provided the first confirmed discoveries of binary asteroids in the near-Earth population. The physical and orbital properties of four near-Earth binary systems are described in detail. Additional information is contained in the original extended abstract.

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Summers, Jerry C. (Inventor); Davis, Patricia P. (Inventor); Oglesby, Donald M. (Inventor); Schryer, Jacqueline L. (Inventor); Gulati, Suresh T. (Inventor)

2011-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Effect of thermally growth oxides (TGO) on adhesion strength for high purity yitria stabilised zirconia (YSZ) and rare - Earth lanthanum zirconates (LZ) multilayer thermal barrier coating before and after isothermal heat treatment

NASA Astrophysics Data System (ADS)

Yunus, Salmi Mohd; Johari, Azril Dahari; Husin, Shuib

2017-12-01

Investigation on the effect of Thermally Growth Oxides (TGO) on the adhesion strength for thermal barrier coating (TBC) was carried out. The TBC under studied was the multilayer systems which consist of NiCrAlY bond coat and YSZ/LZ ceramic coating deposited on Ni-based superalloy substrates. The development of thermally growth oxides (TGO) for both TBC systems after isothermal heat treatment was measured. Isothermal heat treatment was carried out at 1100 ˚C for 100 hours to age the samples. ASTM D4541: Standard Test Method for Pull-off Strength of Coatings using Portable Adhesion Tester was used to measure the adhesion strength of both TBC systems before and after heat treatment. The effect of the developed TGO on the measured adhesion strength was examined and correlation between them was established individually for both TBC systems. The failure mechanism of the both system was also identified; either cohesive or adhesive or the combination of both. The results showed that TGO has more than 50% from the bond coat layer for rare-earth LZ system compared to the typical YSZ system, which was less than 10 % from the bond coat layer. This leads to the lower adhesion strength of rare-earth LZ coating system compared to typical YSZ system. Failure mechanism during the pull-off test also was found to be different for both TBC systems. The typical YSZ system experienced cohesive failure whereas the rare-earth LZ system experienced the combination of cohesive and adhesive failure.

Oxidation and protection of fiberglass-epoxy composite masts for photovoltaic arrays in the low Earth orbital environment

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Paulsen, Phillip E.; Brady, Joyce A.; Ciancone, Michael L.

1988-01-01

Fiberglass-epoxy composites are considered for use as structural members for the mast of the space station solar array panel. The low Earth orbital environment in which space station is to operate is composed mainly of atomic oxygen, which has been shown to cause erosion of many organic materials and some metals. Ground based testing in a plasma asher was performed to determine the extent of degradation of fiberglass-epoxy composites when exposed to a simulated atomic oxygen environment. During exposure, the epoxy at the surface of the composite was oxidized, exposing individual glass fibers which could easily be removed. Several methods of protecting the composite were evaluated in an atomic oxygen environment and with thermal cycling and flexing. The protection techniques evaluated to date include an aluminum braid covering, an indium-tin eutectic and a silicone based paint. The open aluminum braid offered little protection while the CV-1144 coating offered some initial protection against atomic oxygen, but appears to develop cracks which accelerate degradation when flexed. Coatings such as the In-Sn eutectic may provide adequate protection by containing the glass fibers even though mass loss still occurs.

GJ 581 update: Additional evidence for a Super-Earth in the habitable zone

NASA Astrophysics Data System (ADS)

Vogt, S. S.; Butler, R. P.; Haghighipour, N.

2012-08-01

We present an analysis of the significantly expanded HARPS 2011 radial velocity data set for GJ 581 that was presented by Forveille et al. (2011). Our analysis reaches substantially different conclusions regarding the evidence for a Super-Earth-mass planet in the star's Habitable Zone. We were able to reproduce their reported χν2 and RMS values only after removing some outliers from their models and refitting the trimmed down RV set. A suite of 4000 N-body simulations of their Keplerian model all resulted in unstable systems and revealed that their reported 3.6σ detection of e=0.32 for the eccentricity of GJ 581e is manifestly incompatible with the system's dynamical stability. Furthermore, their Keplerian model, when integrated only over the time baseline of the observations, significantly increases the χν2 and demonstrates the need for including non-Keplerian orbital precession when modeling this system. We find that a four-planet model with all of the planets on circular or nearly circular orbits provides both an excellent self-consistent fit to their RV data and also results in a very stable configuration. The periodogram of the residuals to a 4-planet all-circular-orbit model reveals significant peaks that suggest one or more additional planets in this system. We conclude that the present 240-point HARPS data set, when analyzed in its entirety, and modeled with fully self-consistent stable orbits, by and of itself does offer significant support for a fifth signal in the data with a period near 32 days. This signal has a false alarm probability of <4 % and is consistent with a planet of minimum mass 2.2 M_⊙, orbiting squarely in the star's habitable zone at 0.13 AU, where liquid water on planetary surfaces is a distinct possibility.

Launch vehicles of the future - Earth to near-earth space

NASA Astrophysics Data System (ADS)

Keyworth, G. A., II

Attention is given to criteria for launch vehicles of the future, namely, cost, flexibility of payload size, and routine access to space. The National Aerospace Plane (NASP), an airplane designed to achieve hypersonic speeds using a sophisticated air-breathing engine, is argued to meet these criteria. Little additional oxygen is needed to enter low-earth orbit, and it will return to an airport runway under powered flight. Cost estimates for a NASP-derived vehicle are two to five million dollars for a payload of 20,000 to 30,000 pounds to orbit. For the Shuttle, a comparable payload is nominally about 150 million dollars. NASP estimates for the new single-stage-to-orbit designs are substantially lower than existing launch costs. The NASP also offers fast turnaround and minimal logistics. Access to virtually all near-earth orbits will be provided as well.

Melting and vibrational properties of planetary materials under deep Earth conditions

NASA Astrophysics Data System (ADS)

Jackson, Jennifer

2013-06-01

The large chemical, density, and dynamical contrasts associated with the juxtaposition of a liquid iron-dominant alloy and silicates at Earth's core-mantle boundary (CMB) are associated with a rich range of complex seismological features. For example, seismic heterogeneity at this boundary includes small patches of anomalously low sound velocities, called ultralow-velocity zones. Their small size (5 to 40 km thick) and depth (about 2800 km) present unique challenges for seismic characterization and geochemical interpretation. In this contribution, we will present recent nuclear resonant inelastic x-ray scattering measurements on iron-bearing silicates, oxides, and metals, and their application towards our understanding of Earth's interior. Specifically, we will present measurements on silicates and oxide minerals that are important in Earth's upper and lower mantles, as well as iron to over 1 megabar in pressure. The nuclear resonant inelastic x-ray scattering method provides specific vibrational information, e.g., the phonon density of states, and in combination with compression data permits the determination of sound velocities and other vibrational information under high pressure and high temperature. For example, accurate determination of the sound velocities and density of chemically complex Earth materials is essential for understanding the distribution and behavior of minerals and iron-alloys with depth. The high statistical quality of the data in combination with high energy resolution and a small x-ray focus size permit accurate evaluation of the vibrational-related quantities of iron-bearing Earth materials as a function of pressure, such as the Grüneisen parameter, thermal pressure, sound velocities, and iron isotope fractionation quantities. Finally, we will present a novel method detecting the solid-liquid phase boundary of compressed iron at high temperatures using synchrotron Mössbauer spectroscopy. Our approach is unique because the dynamics of

Improving the lipid profile of ready-to-cook meat products by addition of omega-3 microcapsules: effect on oxidation and sensory analysis.

PubMed

Pérez-Palacios, Trinidad; Ruiz-Carrascal, Jorge; Jiménez-Martín, Estefanía; Solomando, Juan Carlos; Antequera, Teresa

2018-04-15

The omega-3 enrichment of ready-to-cook meat products by microencapsulated fish oil (MFO) addition was analyzed. Accordingly, three batches of chicken nuggets were prepared: (i) control (C); (ii) enriched in bulk fish oil (BFO); and (iii) with added MFO. Sensory features, acceptability, oxidative stability and volatile compounds were analyzed. MFO nuggets did not differ from C ones with respect to any sensory trait. BFO showed increased juiciness and saltiness but decreased meat flavor. Acceptability was not affected by enrichment. Consumers were not able to differentiate between C and MFO in a triangle test, although they could clearly identify BFO nuggets. Higher levels of lipid and protein oxidation indicators and of volatile compounds from fatty acid oxidation were found in BFO nuggets compared to C and MFO nuggets. Enrichment of ready-to-cook meat products in omega-3 fatty acids with MFO provides both lipid and protein oxidative protection without changes in sensory quality. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Supporting Inquiry-based Earth System Science Instruction with Middle and High School Earth Science Teachers

NASA Astrophysics Data System (ADS)

Finkel, L.; Varner, R.; Froburg, E.; Smith, M.; Graham, K.; Hale, S.; Laura, G.; Brown, D.; Bryce, J.; Darwish, A.; Furman, T.; Johnson, J.; Porter, W.; von Damm, K.

2007-12-01

The Transforming Earth System Science Education (TESSE) project, a partnership between faculty at the University of New Hampshire, Pennsylvania State University, Elizabeth City State University and Dillard University, is designed to enrich the professional development of in-service and pre-service Earth science teachers. One goal of this effort is to help teachers use an inquiry-based approach to teaching Earth system science in their classrooms. As a part of the TESSE project, 42 pre-service and in-service teachers participated in an intensive two-week summer institute at UNH taught by Earth scientists and science educators from TESSE partnership institutions. The institute included instruction about a range of Earth science system topics as well as an introduction to teaching Earth science using an inquiry-based approach. In addition to providing teachers with information about inquiry-based science teaching in the form of sample lesson plans and opportunities to revise traditional lessons and laboratory exercises to make them more inquiry-based, TESSE instructors modeled an inquiry- based approach in their own teaching as much as possible. By the end of the Institute participants had developed lesson plans, units, or year-long course overviews in which they were expected to explain the ways in which they would include an inquiry-based approach in their Earth science teaching over the course of the school year. As a part of the project, graduate fellows (graduate students in the earth sciences) will work with classroom teachers during the academic year to support their implementation of these plans as well as to assist them in developing a more comprehensive inquiry-based approach in the classroom.

Effect of deep discharge on the electrochemical behavior of cobalt oxides and oxyhydroxides used as conductive additives in Ni-MH cells

NASA Astrophysics Data System (ADS)

Douin, Myriam; Guerlou-Demourgues, Liliane; Goubault, Lionel; Bernard, Patrick; Delmas, Claude

When used as conductive additive at the positive electrode of Ni-MH batteries, the Na 0.6CoO 2 phase is converted, during the first charge, by oxidation, in a γ-hydrated cobalt oxyhydroxide, which exhibits promising performances. The behavior of these phases was studied in specific deep discharge or low potential storage conditions, through electrochemical short-circuit experiments. The evolution of the electrodes during the cycling was followed by X-ray diffraction and SEM analysis. These novel additives appear to be more efficient in these extreme conditions than the CoO or Co(OH) 2 additives, commonly used in industrial devices.

Short-term nitrous oxide profile dynamics and emissions response to water, nitrogen and carbon additions in two tropical soils

Treesearch

A. D. Nobre; M. Keller; P. M. Crill; R. C. Harriss

2001-01-01

Tropical soils are potentially the highest and least studied nitrous oxide (N2O) production areas in the world. The effect of water, nitrate and glucose additions on profile concentrations and episodic emissions of N2O for two volcanic soils in Costa Rica was examined. Magnitudes of episodic N2O pulses, as well as overall N2O emissions, varied considerably and...

In Situ Electrochemical Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation

DOE PAGES

Chen, Wei; Wang, Haotian; Li, Yuzhang; ...

2015-07-15

The development of catalysts with earth-abundant elements for efficient oxygen evolution reactions is of paramount significance for clean and sustainable energy storage and conversion devices. Our group demonstrated recently that the electrochemical tuning of catalysts via lithium insertion and extraction has emerged as a powerful approach to improve catalytic activity. Here we report a novel in situ electrochemical oxidation tuning approach to develop a series of binary, ternary, and quaternary transition metal (e.g., Co, Ni, Fe) oxides from their corresponding sulfides as highly active catalysts for much enhanced water oxidation. The electrochemically tuned cobalt–nickel–iron oxides grown directly on the three-dimensionalmore » carbon fiber electrodes exhibit a low overpotential of 232 mV at current density of 10 mA cm –2, small Tafel slope of 37.6 mV dec –1, and exceptional long-term stability of electrolysis for over 100 h in 1 M KOH alkaline medium, superior to most non-noble oxygen evolution catalysts reported so far. The materials evolution associated with the electrochemical oxidation tuning is systematically investigated by various characterizations, manifesting that the improved activities are attributed to the significant grain size reduction and increase of surface area and electroactive sites. This work provides a promising strategy to develop electrocatalysts for large-scale water-splitting systems and many other applications.« less

An Earth with affinities to Enstatite Chondrites

NASA Astrophysics Data System (ADS)

McDonough, W. F.

2015-12-01

parent body. The Earth accreted early in a reduced state, perhaps to the point of differentiating silicides into the core. Later accreted material was increasingly more oxidized. Stirring and mixing in the early solar system created opportunities for the Earth and enstatite chondrites to share some, but not all chemical and isotopic characteristics.

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe-oxide (Fe-P-REE) systems

NASA Astrophysics Data System (ADS)

Gleason, James D.; Marikos, Mark A.; Barton, Mark D.; Johnson, David A.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium isotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, ɛ Nd for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of the same age (ɛ Nd = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, ɛ Nd for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks (-1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks (ɛ Nd = -2.0 to -4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar ɛ Nd (-1.7 to -2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with ɛ Nd = -2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.

Arecibo Radar Observations of Near-Earth Asteroids

NASA Astrophysics Data System (ADS)

Rivera-Valentin, Edgard G.; Taylor, Patrick A.; Virkki, Anne; Saran Bhiravarasu, Sriram; Venditti, Flaviane; Zambrano-Marin, Luisa Fernanda; Aponte-Hernandez, Betzaida

2017-10-01

The Arecibo S-Band (2.38 GHz, 12.6 cm; 1 MW) planetary radar system at the 305-m William E. Gordon Telescope in Arecibo, Puerto Rico is the most active, most powerful, and most sensitive planetary radar facility in the world. As such, Arecibo is vital for post-discovery characterization and orbital refinement of near-Earth asteroids. Since August 2016, the program has observed 100 near-Earth asteroids (NEAs), of which 38 are classified as potentially hazardous to Earth and 31 are compliant with the NASA Near-Earth Object Human Space Flight Accessible Targets Study (NHATS). Arecibo observations are critical for identifying NEAs that may be on a collision course with Earth in addition to providing detailed physical characterization of the objects themselves in terms of size, shape, spin, and surface properties, which are valuable for assessing impact mitigation strategies. Here, we will present a sampling of the asteroid zoo observed by Arecibo, including press-noted asteroids 2014 JO25 and the (163693) Atira binary system.

Iron-magnesium alloy in the Earth's Core

NASA Astrophysics Data System (ADS)

Dubrovinskaia, N.; Dubrovinsky, L.; Abrikosov, I.

2005-12-01

Composition of the Earth's outer core is a geochemical parameter crucial for understanding the evolution and current dynamics of our planet. Since it was recognized that the liquid metallic outer core is about 10% less dense than pure iron, different elements lighter than iron, including Si, S, O, C, and H, were proposed as major or at least significantly abundant in Earth's core. However, combination of experimental results with theoretical and geochemical considerations shows that it is unlikely that any one of these elements can account for the density deficit on its own. In series of experiments in a multianvil apparatus and in electrically- and laser-heated diamond anvil cells, we demonstrate that high pressure promotes solubility of magnesium in iron and at megabar pressure range more than 10 at% of Mg can dissolve in Fe. At pressures above 95 to 100 GPa, molten iron reacts with periclase MgO forming an iron-magnesium alloy and iron oxide. Our observations suggest that magnesium can be an important light element in Earth's outer core, but it cannot account for the seismologically determined density deficit on its own.

THE GJ1214 SUPER-EARTH SYSTEM: STELLAR VARIABILITY, NEW TRANSITS, AND A SEARCH FOR ADDITIONAL PLANETS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berta, Zachory K.; Charbonneau, David; Bean, Jacob

2011-07-20

The super-Earth GJ1214b transits a nearby M dwarf that exhibits a 1% intrinsic variability in the near-infrared. Here, we analyze new observations to refine the physical properties of both the star and planet. We present three years of out-of-transit photometric monitoring of the stellar host GJ1214 from the MEarth Observatory and find the rotation period to be long, most likely an integer multiple of 53 days, suggesting low levels of magnetic activity and an old age for the system. We show that such variability will not pose significant problems to ongoing studies of the planet's atmosphere with transmission spectroscopy. Wemore » analyze two high-precision transit light curves from ESO's Very Large Telescope (VLT) along with seven others from the MEarth and Fred Lawrence Whipple Observatory 1.2 m telescopes, finding physical parameters for the planet that are consistent with previous work. The VLT light curves show tentative evidence for spot occultations during transit. Using two years of MEarth light curves, we place limits on additional transiting planets around GJ1214 with periods out to the habitable zone of the system. We also improve upon the previous photographic V-band estimate for the star, finding V = 14.71 {+-} 0.03.« less

Large Ripples on Earth and Mars

NASA Technical Reports Server (NTRS)

Williams, S. H.; Zimbelman, J. R.; Ward, A. W.

2002-01-01

Aeolian ripples on Earth with wavelengths greater than 50 cm have distinctive attributes, that should be helpful in interpreting ripple-like features on Mars. Additional information is contained in the original extended abstract.

Refractive indices of Early Earth organic aerosol analogs

NASA Astrophysics Data System (ADS)

Gavilan, L.; Carrasco, N.; Fleury, B.; Vettier, L.

2017-09-01

Organic hazes in the early Earth atmosphere are hypothesized to provide additional shielding to solar radiation. We simulate the conditions of this primitive atmosphere by adding CO2 to a N2:CH4 gas mixture feeding a plasma. In this plasma, solid organic films were produced simulating early aerosols. We performed ellipsometry on these films from the visible to the near-ultraviolet range. Such measurements reveal how organic aerosols in the early Earth atmosphere preferentially absorb photons of shorter wavelengths than typical Titan tholins, suggesting a coolant role in the early Earth.

Synchrotron-based FTIR microspectroscopy for the mapping of photo-oxidation and additives in acrylonitrile-butadiene-styrene model samples and historical objects.

PubMed

Saviello, Daniela; Pouyet, Emeline; Toniolo, Lucia; Cotte, Marine; Nevin, Austin

2014-09-16

Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-μFTIR) was used to map photo-oxidative degradation of acrylonitrile-butadiene-styrene (ABS) and to investigate the presence and the migration of additives in historical samples from important Italian design objects. High resolution (3×3 μm(2)) molecular maps were obtained by FTIR microspectroscopy in transmission mode, using a new method for the preparation of polymer thin sections. The depth of photo-oxidation in samples was evaluated and accompanied by the formation of ketones, aldehydes, esters, and unsaturated carbonyl compounds. This study demonstrates selective surface oxidation and a probable passivation of material against further degradation. In polymer fragments from design objects made of ABS from the 1960s, UV-stabilizers were detected and mapped, and microscopic inclusions of proteinaceous material were identified and mapped for the first time. Copyright © 2014 Elsevier B.V. All rights reserved.

Mapping the Iron Oxidation State in Martian Meteorites

NASA Technical Reports Server (NTRS)

Martin, A. M.; Treimann, A. H.; Righter, K.

2017-01-01

Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

Rare earth element recycling from waste nickel-metal hydride batteries.

PubMed

Yang, Xiuli; Zhang, Junwei; Fang, Xihui

2014-08-30

With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Virginia Earth Science Collaborative: Developing Highly Qualified Teachers

NASA Astrophysics Data System (ADS)

Cothron, J.

2007-12-01

A collaborative of nine institutes of higher education and non-profits and seventy-one school divisions developed and implemented courses that will enable teachers to acquire an Add-On Earth Science endorsement and to improve their skills in teaching Earth Science. For the Earth Science Endorsement, the five courses and associated credits are Physical Geology (4), Geology of Virginia (4), Oceanography (4), Astronomy (3) and Meteorology (3). The courses include rigorous academic content, research-based instructional strategies, laboratory experiences, and intense field experiences. In addition, courses were offered on integrating new technologies into the earth sciences, developing virtual field trips, and teaching special education students. To date, 39 courses have been offered statewide, with over 560 teachers participating. Teachers showed increased conceptual understanding of earth science topics as measured by pre-post tests. Other outcomes include a project website, a collaborative of over 60 IHE and K-12 educators, pilot instruments, and a statewide committee focused on policy in the earth sciences.

Adsorption of tetracycline on Fe (hydr)oxides: effects of pH and metal cation (Cu2+, Zn2+ and Al3+) addition in various molar ratios

PubMed Central

Hsu, Liang-Ching; Liu, Yu-Ting; Syu, Chien-Hui; Huang, Mei-Hsia; Teah, Heng Yi

2018-01-01

Iron (Fe) (hydr)oxides control the mobility and bioavailability of tetracycline (TC) in waters and soils. Adsorption of TC on Fe (hydr)oxides is greatly affected by polyvalent metals; however, impacts of molar metal/TC ratios on TC adsorptive behaviours on Fe (hydr)oxides remain unclear. Results showed that maximum TC adsorption on ferrihydrite and goethite occurred at pH 5–6. Such TC adsorption was generally promoted by the addition of Cu2+, Zn2+ and Al3+. The greatest increase in TC adsorption was found in the system with molar Cu/TC ratio of 3 due to the formation of Fe hydr(oxide)–Cu–TC ternary complexes. Functional groups on TC that were responsible for the complexation with Cu2+shifted from phenolic diketone groups at Cu/TC molar ratio < 1 to amide groups at Cu/TC molar ratio ≥ 1. For the addition of Al3+, the complexation only took place with phenolic diketone groups, resulting in the enhanced TC adsorption at a molar Al/TC ratio of 1. However, TC adsorption decreased for Al/TC molar ratio > 1 as excess Al3+ led to the competitive adsorption with Al/TC complexes. For the Zn2+ addition, no significant correlation was found between TC adsorption capacity and molar Zn/TC ratios. PMID:29657795

Habitability of the Paleo-Earth as a Model for Earth-like Exoplanets

NASA Astrophysics Data System (ADS)

Mendez, A.

2013-05-01

The Phanerozoic is the current eon of Earth's geological history, from 542 million years ago to today, when large and complex life started to populate the ocean and land areas. Our planet became more hospitable and life took the opportunity to evolve and spread globally, especially on land. This had an impact on surface and atmospheric bio-signatures. Future observations of exoplanets might be able to detect similar changes on nearby exoplanets. Therefore, the application of the evolution of terrestrial habitability might help to determine the potential for life on Earth-like exoplanets. Here we evaluated the habitability of Earth during the Phanerozoic as a model for comparison with future observations of Earth-like exoplanets. Vegetation was used as a global indicator of habitability because as a primary producer it provides the energy for many other simple to complex life forms in the trophic scale. Our first proxy for habitability was the Relative Vegetation Density (RVD) derived from our vegetation datasets of the Visible Paleo-Earth. The RVD is a measure similar to vegetation indices, such as the Normalized Difference Vegetation Index (NDVI), that gives a general idea of the global area-weighted fraction of vegetation cover. Our second habitability proxy was the Standard Primary Habitability (SPH) derived from mean global surface temperatures and relative humidity. The RVD is a more direct measure of the habitability of a planet but the SPH is easier to measure by remote sensors. Our analysis shows that terrestrial habitability has been greater than today for most of the Phanerozoic as demonstrated by both the RVD and SPH, with the Devonian and Cretaceous particularly more habitable. The RVD and SPH are generally correlated except around the Permian-Triassic, matching the P-Tr extinction. There has been a marked decrease in terrestrial habitability during the last 100 million years, even superseding the K-Pg extinction. Additional metrics were used to examine

Experimental study of heterogeneous organic chemistry induced by far ultraviolet light: Implications for growth of organic aerosols by CH3 addition in the atmospheres of Titan and early Earth

NASA Astrophysics Data System (ADS)

Hong, Peng; Sekine, Yasuhito; Sasamori, Tsutoni; Sugita, Seiji

2018-06-01

Formation of organic aerosols driven by photochemical reactions has been observed and suggested in CH4-containing atmospheres, including Titan and early Earth. However, the detailed production and growth mechanisms of organic aerosols driven by solar far ultraviolet (FUV) light remain poorly constrained. We conducted laboratory experiments simulating photochemical reactions in a CH4sbnd CO2 atmosphere driven by the FUV radiations dominated by the Lyman-α line. In the experiments, we analyzed time variations in thickness and infrared spectra of solid organic film formed on an optical window in a reaction cell. Gas species formed by FUV irradiation were also analyzed and compared with photochemical model calculations. Our experimental results show that the growth rate of the organic film decreases as the CH4/CO2 ratio of reactant gas mixture decreases, and that the decrease becomes very steep for CH4/CO2 < 1. Comparison with photochemical model calculations suggests that polymerizations of gas-phase hydrocarbons, such as polyynes and aromatics, cannot account for the growth rate of the organic film but that the addition reaction of CH3 radicals onto the organic film with the reaction probability around 10-2 can explain the growth rate. At CH4/CO2 < 1, etching by O atom formed by CO2 photolysis would reduce or inhibit the growth of the organic film. Our results suggest that organic aerosols would grow through CH3 addition onto the surface during the precipitation of aerosol particles in the middle atmosphere of Titan and early Earth. On Titan, effective CH3 addition would reduce C2H6 production in the atmosphere. On early Earth, growth of aerosol particles would be less efficient than those on Titan, possibly resulting in small-sized monomers and influencing UV shielding.

Hydrostatic figure of the earth: Theory and results

NASA Technical Reports Server (NTRS)

Khan, M. A.

1973-01-01

The complete development of the mathematical theory of hydrostatic equilibrium for the earth is recounted. Modifications of the first order theory are given along with the subsequent extension to the second order. In addition, the equations are presented which resulted from a revision of the second order theory to suit the new applications and data types of the post-artificial earth satellite era.

Problems with the thermogravimetric determination of oxygen stoichiometries in pure and rare-earth substituted La2RuO5

NASA Astrophysics Data System (ADS)

Riegg, S.; Müller, T.; Ebbinghaus, S. G.

2013-06-01

The oxygen stoichiometries of pure and rare-earth substituted La2RuO5 have been investigated by thermogravimetry (TG) in reducing atmosphere. Assuming that the observed total weight loss is caused by the reduction of Ru4+ to Ru-metal, remarkable oxygen deficiencies were calculated. These would correspond to ruthenium oxidation states significantly lower than the ones experimentally observed by XANES. To explain this discrepancy we investigated the reduction products by X-ray absorption spectroscopy (XAS). EXAFS measurements at the Ru-K edge revealed the presence of an X-ray amorphous ruthenium oxide, indicating an incomplete reduction. The apparent oxygen deficiencies obtained for pure and rare-earth substituted samples correlate with the amount of remaining ruthenium oxide. The presence of a ruthenium oxide species was furthermore verified by Ru-LIII XANES investigations. Our results show that the determination of oxygen contents by thermogravimetry might fail even for the easily reducable nobel metal oxides and therefore has to be applied with caution if the reaction products cannot be identified unambiguously.

The size distribution of the earth-approaching asteroids

NASA Technical Reports Server (NTRS)

Rabinowitz, D. L.

1993-01-01

The discovery circumstances of the first asteroids ever observed outside the earth's atmosphere but within the neighborhood of the earth-moon system are described. Four natural objects with diameters in the range 5-50 m were detected during a search for earth-approaching asteroids conducted each month at the 0.91-m Spacewatch Telescope at Kitt Peak. An additional 19 earth approachers with sizes in the range 50 m to 5 km were discovered. These obervations determine the cumulative flux of asteroids near earth as a function of absolute magnitude. For asteroids larger than about 100 m, a power-law dependence with exponent of about 0.9 is observed, consistent with their evolution from the main-belt population. At about 10 m, the flux is more than two orders of magnitude greater than this power-law extrapolation.

A novel methodology for rapid digestion of rare earth element ores and determination by microwave plasma-atomic emission spectrometry and dynamic reaction cell-inductively coupled plasma-mass spectrometry.