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Rb-Sr and Sm-Nd isotope geochemistry and chronology of cherts from the Onverwacht Group (3.5 AE), South Africa

An Rb-Sr and Sm-Nd isotopic analysis of Archean chert samples from the Onverwacht Group, South Africa is presented, showing the same characteristic Rb and Sr concentrations as Phanerozoic cherts, with a very large range of Rb-87/Sr-86 ratios. A good correlation line in the Rb-87 to Sr-87 evolution diagram, corresponding to an age of about 2119 My and an initial Sr-87/Sr-86 ratio of about 0.72246, is derived which may be interpreted as reflecting the age of rehomogenization of the Sr in the protolith and the recrystallization of these cherts due to circulating hydrothermal fluids during regional metamorphism about 1.4 AE after deposition of the Onverwacht Group. The Sm-Nd systematics reflect an ancient source age of about 3.5 AE.

Weis, D.↗

Decoupled Rb-Sr and Sm-Nd isotopic evolution of the continental crust

Evidence was presented that the Rb-Sr and Sm-Nd isotopic systems are decoupled in crust-mantle evolution. Rare earth element (including Sm and Nd) residue principally in silicates, and are resistant to mobilization by weathering and metamorphism. In contrast, Rb and Sr are easily fractionated by crustal processes and residue in carbonates as well as in silicates. As a result, continental Sr, but not Nd, can be recycled into the mantle by exchange of seawater with basalt at spreading ridges and by subduction of carbonates associated with ridge processes. These effects result in mean Rb-Sr ages of the continental crust and of the upper mantle that are too young. Crustal growth curves based largely on Rb-Sr data, such that of Hurley and Rand, are therefore incorrect.

Goldstein, S. L.↗

Initial Sr-87/Sr-86 and Sm-Nd chronology of chondritic meteorites

Isotopic analyses of the Rb-Sr and Sm-Nd systems in phosphates from ordinary chondritic meteorites (Bjurbole, Mocs, Menow, Elenovka, Ambapur Nagla, and St. Severin) are presented. The Sm-Nd data yield an isochron of age 4.55 + or - 0.45 Ga and an initial Nd-143/Nd-144 consistent with that of Juvinas. Initial Sr-87/Sr-86 ratios are characteristically (possibly excepting St. Severin) elevated with respect to BABI or ALL. Considering both presently and previously reported data, elevation of initial Sr-87/Sr-86 ratios corresponding to metamorphism intervals of the order of 10 to the 8th years seems quite characteristic of chondrites of metamorphic grade 4 or higher. These formation intervals, however, do not correlate with either degree of metamorphism or with I-Xe ages, hence such data for metamorphic chronologies should be interpreted with caution.

Brannon, J. C.↗

The Estherville mesosiderite - U-Pb, Rb-Sr, and Sm-Nd isotopic study of a polymict breccia

The U-Pb, Rb-Sr, and Sm-Nd isotopic systematics of the Estherville mesoderite were studied using analytical procedures and mass spectrometric techniques similar to those reported by Nakamura et al. (1976), Tatsumoto et al. (1987), and Premo et al. (1989) to analyze 21 separates of a 13-g Estherville clast, obtained either by handpicking or by using density and magnetic separation methods. The results on the Pb-Pb and U-Pb ages (about 4555 and about 4560 Ma, respectively) indicate that at least a part of the Estherville silicate fraction was formed early in the history of solar system. Younger Pb-Pb and U-Pb ages (about 4.43 Ga) were also obtained, confirming the heterogeneity of the Estherville mesoderite that is in agreement with the Wasson and Rubin (1985) suggestion of several generations of meteoritic impacts. The Sm-Nd and Rb-Sr ages were found to be close to 4.56 Ga.

Brouxel, M.↗

s-process Ba, Nd, and Sm in presolar SiC from the Murchison meteorite

Ion microprobe isotopic measurements of Ba, Nd, and Sm in the K-series SiC size separates on which noble gas measurements were made by Lewis et al. (1990) are reported. All elements show isotopic abundance patterns characteristic for the s-process. The Ba-134/Ba-136 ratios are distinct from solar, indicating that s-Ba in SiC is different from that in the solar system. Ba-138/Ba-136 ratios decrease with grain size; if interpreted as being due to different neutron exposures, this trend is opposite of that shown by the Kr-86/Kr-82 ratios. Although other isotropic ratios for Ba and those for Nd and Sm differ in detail from theoretical predictions, the disagreements probably being due to uncertainties in the n-capture cross sections and simplifications in the models, the general agreement of the data with models of s-process nucleosynthesis support an AGB star origin for the relatively fine-grain SiC under consideration. Ba-136 in SiC is up to 85 percent pure s-process.

Zinner, Ernst↗

The U-Th-Pb, Sm-Nd, and Ar-Ar isotopic systematics of lunar meteorite Yamato-793169

U-Th-Pb, Sm-Nd, and (Ar-40)-(Ar-39) isotopic studies were performed on Yamato (Y)-793169, an unbrecciated diabasic lunar meteorite whose chemical composition is close to low Ti(LT) and very low-Ti (VLT) mare basalts. The isotopic data indicate that the meteorite was formed earlier than 3.9 Ga from a source with low U/Pb and high Sm/Nd and was distributed by a thermal event at 751 Ma. due to the small sample size (104 mg), a plagioclase crystal and glass grains were handpicked for Ar analysis, leaving four fractions for the U-Th-Pb and Sm-Nd studies; a fine-grained fraction (less than 63 microns; Fine) and three medium-grained fractions (63-150 microns). Medium-grained fractions were divided by density; a heavy fraction (rho greater than 3.3) consisting mainly of pyroxene (PX1), a lighter fraction (rho less than 2.8) consisting of plagioclase (PL), and a middle density fraction (predominantly pyroxene; PX2). The fractions were washed with acetone and alcohol, and then leached in 0.01 HBr and 0.1N HBr in order to remove any terrestrial Pb contamination. Analysis of the HBr leaches revealed that this meteorite was heavily contaminated with terrestrial Pb during its residence in Antarctic ice.

Torigoye, Noriko↗

Rb-Sr and Sm-Nd Isotopic Studies of Shergottite Y980459 and a Petrogenetic Link Between Depleted Shergottites and Nakhlites

Y980459 was found near the Minami-Yamato Nunataks, Antarctica in 1998 and was recently classified as an olivine-bearing shergottite. It petrographically resembles many other olivine-phyric shergottites mostly found in hot deserts, e.g. DaG476/489, SaU005/094, Dohfar 019, NWA 1068/1110, NWA 1195 and EETA 79001 lith.A. However, Y980459 is unique among these meteorites in several respects. It is apparently very fresh and only weakly shocked. Also, it completely lacks plagioclase, but contains abundant residual volcanic glass. This group of olivine-phyric shergottites is characterized by variable crystallization ages from approx.172 Ma to approx.575 Ma and ejection ages from approx.1 Ma to approx.20 Ma. They probably represent volcanic melts originated from the deep Martian mantle. We performed Rb-Sr and Sm-Nd isotopic analyses on Y980459 to determine its crystallization age and compared its age and isotopic signatures with those obtained from other olivine-phyric shergottites and QUE 94201, the other Antarctic olivine-free shergottite. QUE 94201 and some olivine-phyric shergottites e.g. DaG, SaU, Doh and EETA lith A have similar depleted-LREE patterns and are herein referred to as depleted shergottites. A petrogenetic model correlating depleted shergottites and nakhlites is also proposed. Preliminary Rb-Sr and Sm-Nd isotopic data for Y980459 were presented earlier at the NIPR, Japan, in 2003.

Shih, C.-Y.↗

REE chemistry and Sm-Nd systematics of late Archean weathering profiles in the Fortescue Group, Western Australia

Two weathering profiles, each consisting of an upper, sericite-rich zone and a lower, chlorite-rich zone, are preserved between flows of the Mt. Roe Basalt in the Fortescue Group, Hamersley Basin, Western Australia. REE concentrations in samples from these two profiles, which originally developed ca 2,760 Ma, show large variations depending on stratigraphic position. LREE abundances and (La/Yb)N are greatest at depths of 3-6 m below the paleosurface of the Mt. Roe #1 profile and are somewhat lower in samples above this level. The LREEs reach concentrations 6-9 times greater than in the underlying basalt, and thus appear to have been mobilized downward in the paleosol and concentrated in its middle part. LREE concentrations in the #2 profile show a similar distribution but with a sharp increase in all REE concentrations within 50 cm of the paleosurface. The distinction between the REE profiles in the two paleosols may be related to the difference in the overlying material. The #1 paleosol is overlain by a few meters of sediments and then by basalt, whereas the #2 paleosol is directly overlain by basalt. The LREEs appear to have been mobilized both during chemical weathering of the parental basalt and during later lower-greenschist-facies metamorphism and metasomatism of the paleosols. Remobilization of the REEs during the regional metamorphism of the Fortescue Group is confirmed by a whole-rock Sm-Nd reference isochron of Mt. Roe #1 samples with an age of 2,151 +/- 360 Ma. Variable initial 143Nd/144Nd values of unweathered basalt samples which may represent the paleosol protolith prevents a confident determination of the magnitude of LREE mobility. Both the initial mobilization of the REEs during weathering and the metasomatic remobilization appear to have taken place under redox conditions where Ce was present dominantly as Ce3+, because Ce anomalies are not developed within the sericite zone samples regardless of concentration. Europium anomalies in the paleoweathering profile are somewhat variable and were probably modified by mobilization of Eu2+ at metamorphic conditions. In all samples, the HREEs appear to have been relatively immobile and correlate with Al, Ti, Cr, V, Zr, and Nb. Sm-Nd systematics and REE patterns of four unweathered basalt samples indicate derivation of the Mt. Roe Basalts from a heterogeneous and enriched source having epsilon Nd between -4.0 and -7.4. Initial 143Nd/144Nd values of these basalts are even lower than those reported by NELSON et al. (1992) for Fortescue Group basalts and indicate a substantial crustal component in the generation of Mt. Roe Basalts.

NASA Discipline Exobiology↗

Rb-Sr and Sm-Nd Isotopic Studies of Lunar Highland Meteorite Y86032 and Lunar Ferroan Anorthosites 60025 and 67075

Lunar meteorite Yamato (Y) 86032 is a feldspathic breccia containing anorthositic fragments similar to ferroan anorthosite (FAN) clasts commonly found in Apollo 16 highland rocks. Previous Ar-39-Ar-40 analyses of a grey anorthositic clast (,116 GC) in Y86032 revealed an old degassing age of 4.39 plus or minus 0.06 Ga, which is as old as crystallization ages of some FANs e.g. 60025, 67016 and 67215, as determined by the more robust Sm-Nd radiometric method. The calculated initial Nd value for the clast is -1.8 plus or minus 0.3 for the age. The old age and its negative initial Nd value indicate that Y86032 contains components of the primitive lunar crust related to the lunar magma ocean (LMO). We undertook further Rb-Sr and Sm-Nd isotopic investigation of three major lithologies in the meteorite as described in the mineralogical and petrological studies. Ar-39-Ar-40 analyses of these component lithologies are presented in this volume. Also, we analyzed two Apollo 16 FANs, 60025 and 67075, to compare their ages and isotopic signatures to Y86032. Y86032 probably came from a feldspathic highland terrane (FHT) on the northern farside highlands, a locality not sampled by the Apollo and Luna missions.

Shih, C.-Y.↗

GIFTS SM EDU Level 1B Algorithms

The Geosynchronous Imaging Fourier Transform Spectrometer (GIFTS) SensorModule (SM) Engineering Demonstration Unit (EDU) is a high resolution spectral imager designed to measure infrared (IR) radiances using a Fourier transform spectrometer (FTS). The GIFTS instrument employs three focal plane arrays (FPAs), which gather measurements across the long-wave IR (LWIR), short/mid-wave IR (SMWIR), and visible spectral bands. The raw interferogram measurements are radiometrically and spectrally calibrated to produce radiance spectra, which are further processed to obtain atmospheric profiles via retrieval algorithms. This paper describes the GIFTS SM EDU Level 1B algorithms involved in the calibration. The GIFTS Level 1B calibration procedures can be subdivided into four blocks. In the first block, the measured raw interferograms are first corrected for the detector nonlinearity distortion, followed by the complex filtering and decimation procedure. In the second block, a phase correction algorithm is applied to the filtered and decimated complex interferograms. The resulting imaginary part of the spectrum contains only the noise component of the uncorrected spectrum. Additional random noise reduction can be accomplished by applying a spectral smoothing routine to the phase-corrected spectrum. The phase correction and spectral smoothing operations are performed on a set of interferogram scans for both ambient and hot blackbody references. To continue with the calibration, we compute the spectral responsivity based on the previous results, from which, the calibrated ambient blackbody (ABB), hot blackbody (HBB), and scene spectra can be obtained. We now can estimate the noise equivalent spectral radiance (NESR) from the calibrated ABB and HBB spectra. The correction schemes that compensate for the fore-optics offsets and off-axis effects are also implemented. In the third block, we developed an efficient method of generating pixel performance assessments. In addition, a random pixel selection scheme is designed based on the pixel performance evaluation. Finally, in the fourth block, the single pixel algorithms are applied to the entire FPA.

Tian, Jialin↗

Sm-Nd and Rb-Sr Isotopic Studies of Meteorite Kalahari 009: An Old VLT Mare Basalt

Lunar meteorite Kalahari 009 is a fragmental basaltic breccia contain ing various very-low-Ti (VLT) mare basalt clasts embedded in a fine-g rained matrix of similar composition. This meteorite and lunar meteorite Kalahari 008, an anorthositic breccia, were suggested to be paired mainly due to the presence of similar fayalitic olivines in fragment s found in both meteorites. Thus, Kalahari 009 probably represents a VLT basalt that came from a locality near a mare-highland boundary r egion of the Moon, as compared to the typical VLT mare basalt samples collected at Mare Crisium during the Luna-24 mission. The concordant Sm-Nd and Ar-Ar ages of such a VLT basalt (24170) suggest that the extrusion of VLT basalts at Mare Crisium occurred 3.30 +/- 0.05 Ga ag o. Previous age results for Kalahari 009 range from approximately 4.2 Ga by its Lu-Hf isochron age to 1.70?0.04 Ga of its Ar-Ar plateau ag e. However, recent in-situ U-Pb dating of phosphates in Kalahari 009 defined an old crystallization age of 4.35+/- 0.15 Ga. The authors su ggested that Kalahari 009 represents a cryptomaria basalt. In this r eport, we present Sm-Nd and Rb-Sr isotopic results for Kalahari 009, discuss the relationship of its age and isotopic characteristics to t hose of other L-24 VLT mare basalts and other probable cryptomaria ba salts represented by Apollo 14 aluminous mare basalts, and discuss it s petrogenesis.

Shih, C.-Y.↗

OTF CCSDS SM and C Interoperability Prototype

A presentation is provided to demonstrate the interoperability between two space flight Mission Operation Centers (MOCs) and to emulate telemetry, actions, and alert flows between the two centers. One framework uses a COTS C31 system that uses CORBA to interface to the local OTF data network. The second framework relies on current Houston MCC frameworks and ad hoc clients. Messaging relies on SM and C MAL, Core and Common Service formats, while the transport layer uses AMS. A centralized SM and C Registry uses HTTP/XML for transport/encoding. The project's status and progress are reviewed.

Reynolds, Walter F.↗

Sol-Gel Synthesis of La(0.6)Sr(0.4)CoO(3-x) and Sm(0.5)Sr(0.5)CoO(3-x) Cathode Nanopowders for Solid Oxide Fuel Cells

Nanopowders of La(0.6)Sr(0.4)CoO(3-x) (LSC) and Sm(0.5)Sr(0.5)CoO(3-x) (SSC) compositions, which are being investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC) with La(Sr)Ga(Mg)O(3-x) (LSGM) as the electrolyte, were synthesized by low-temperature sol-gel method using metal nitrates and citric acid. Thermal decomposition of the citrate gels was followed by simultaneous DSC/TGA methods. Development of phases in the gels, on heat treatments at various temperatures, was monitored by x-ray diffraction. Solgel powders calcined at 550 to 1000 C consisted of a number of phases. Single perovskite phase La(0.6)Sr(0.4)CoO(3-x) or Sm(0.5)Sr(0.5)CoO(3-x) powders were obtained at 1200 and 1300 C, respectively. Morphological analysis of the powders calcined at various temperatures was done by scanning electron microscopy. The average particle size of the powders was approx.15 nm after 700 C calcinations and slowly increased to 70 to 100 nm after heat treatments at 1300 to 1400 C.

Bansal, Narottam P.↗

Role of washing solvents in defining the magnetic performance of Sm 2 Fe 17 N 3 obtained by reduction diffusion

Calciothermic reduction-diffusion (RD) is one of the leading synthesis methods for Sm 2 Fe 17 N 3 (SmFeN), but sintering of such RD-derived powders is hampered by oxidation and CaO byproducts. Here, we systematically evaluate how post-synthesis washing solvents govern powder chemistry and magnetic performance. RD-synthesized SmFeN powder was washed with several aqueous and non-aqueous solvents using identical washing protocols. This was followed by an assessment of both the as-washed powder as well as after annealing at 425 °C. Phase content was quantified by synchrotron PXRD and Rietveld refinement and SEM/EDS. The oxygen content of the powders was determined via inert gas fusion and the magnetization by DC magnetometry. While all aqueous-based solutions were able to remove CaO, the non-aqueous solutions were only effective with extended washing times. Prior to annealing, the crystalline phases and magnetic properties of the as-washed powders were largely the same regardless of washing solvent. However, differences emerge after annealing, where water-based washing markedly lowers the coercivity (H c ~3.8-4.3 kOe). In contrast, non-aqueous NH 4 Cl-methanol washing protocols were more effective in preserving coercivity (H c ~4.9-5.9 kOe). We attribute this to lower oxygen content in the non-aqueous samples (~9,400 ppm v ~6,400 ppm, respectively) which in turn reduced the formation of α-Fe during annealing. These results highlight the importance of solvent choice in washing RD-synthesized SmFeN and demonstrate that non-aqueous protocols, which better limit oxidation, outperform aqueous solvents despite the need for longer washing times.

36 MATERIALS SCIENCE↗

Effect of Co on twin formation and magnetic properties of Sm(Fe,Ti,V) 12 alloys

Transferring the excellent intrinsic magnetic properties of SmFe 12 -based compounds to their extrinsic properties remains the main challenge in the development of high-performance SmFe12-based permanent magnets. Twin formation is one of the reasons for the inability to achieve high coercivity and remanence. Here we have shown that the addition of Co in Sm(Fe 1-x Co x ) 10–11 M 1–2 alloys, where M=Ti and V, leads to an increase in twin density. Microstructural characterizations revealed that the atomic arrangement in the twin boundary changes depending on the stabilizing element, which directly influences the local intrinsic magnetic properties. Theoretical investigations showed that the critical grain size at which twin formation can be hindered by grain size reduction decreases when the stabilizer changes from V to Ti. Furthermore, this study shows that the alloy composition influences not only the intrinsic magnetic properties but also the twin formation energy and its grain size dependence, crucial for the design of SmFe12-based permanent magnets.

36 MATERIALS SCIENCE↗

Crystal Growth of Quaternary RE 2 EuSi 2 S 8 ( RE = Ce–Nd, Sm, Gd, Tb) Using Flux-Assisted Boron Chalcogen Mixture (BCM) Method: Investigation of Magnetic and Luminescence Properties

A series of quaternary rare-earth containing thiosilicates with the general formula RE 2 EuSi 2 S 8 (RE = Ce–Nd, Sm, Gd, Tb) has been synthesized via the flux-assisted boron chalcogen mixture (BCM) crystal growth method. High-quality single crystals were obtained, and their crystal structures were determined by single-crystal X-ray diffraction. The RE 2 EuSi 2 S 8 series crystallizes in the trigonal system, adopting the space group R-3c. Polycrystalline samples were employed for physical property measurements, including magnetic susceptibility measurements, UV–visible diffuse reflectance, and photoluminescent response. Magnetic data of RE 2 EuSi 2 S 8 ( RE = Ce, Nd, and Gd) were collected over the 2–300 K temperature range. The samples were paramagnetic behavior with negative Weiss constants (θ W = −11.05, −10.55, and −1.35 K respectively). Their thermal stability was investigated using thermogravimetric analysis (TGA). Optical band gaps, estimated from diffuse reflectance spectra, were determined to be 2.2(1) eV for Ce 2 EuSi 2 S 8 , 1.8(1) eV for Nd 2 EuSi 2 S 8 , and 1.7(1) eV for Gd 2 EuSi 2 S 8 respectively. Finally, photoluminescence measurements were collected on Ce 2 EuSi 2 S 8 and Tb 2 EuSi 2 S 8 single crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flux-Assisted Boron Chalcogen Mixture (BCM) Method for Synthesizing Mixed Chalcogenide Semiconductors (AkRE 2 Si 2 Se x S 8– x and CaRE 2 Si 2 Se 8 ) ( Ak = Ca and Sr; RE = La, Ce, Pr, Nd, and Sm): Investigation of Their Magnetic and Optical Properties

We report a detailed structural analysis of a series of ten quaternary rare-earth-containing seleno-thiosilicates AkRE 2 Si 2 Se x S 8-x and selenosilicates, CaRE 2 Si 2 Se 8 (Ak = Ca and Sr; RE = La, Ce, Pr, Nd, and Sm). Single crystals were obtained by using the flux-assisted boron chalcogen mixture (BCM) method and single crystal X-ray diffraction was used to determine their structures. All members of the AkRE 2 Si 2 Se x S 8-x and CaRE 2 Si 2 Se 8 series crystallize in the space group R$\bar{3}$c (space group number 167) of the trigonal crystal system. The single-crystal X-ray diffraction analysis revealed a strong preference for Se/S atoms to occupy one vs. the other of the two available sites. Polycrystalline samples were used for magnetic susceptibility and UV–visible diffuse reflectance measurements. Magnetic measurements show that CaCe₂Si₂Se₁.₇₃S₆.₂₇ and CaNd₂Si₂Se₂.₅S₅.₅ are paramagnetic with negative Weiss constants (θ = –60.1 and –26.2). Diffuse reflectance analysis gives optical band gaps of 2.7(1) eV (CaLa₂Si₂Se₂.₃₈S₅.₆₂), 2.2(1) eV (CaCe₂Si₂Se₁.₇₃S₆.₂₇), 2.5(1) eV (CaNd₂Si₂Se₂.₅S₅.₅), and 2.0(1) eV (CaCe₂Si₂Se₈), consistent with density functional theory calculations. By partially or fully replacing S sites with Se it was possible to achieve band gap tuning. Photoluminescence behavior was also investigated for CaCe 2 Si 2 Se 1.73 S 6.27 via irradiation with 375 nm ultraviolet light.

BCM method↗

JOINT APPOINTEE: Evolution of ferroelectric properties in SmxBi1-xFeO3 via automated Piezoresponse Force Microscopy across combinatorial spread libraries

Combinatorial spread libraries offer a innovative approach to explore the evolution of material properties over broad concentration, temperature, and growth parameter spaces. However, traditional limitation of this approach is the requirement for the read-out of functional properties across the library. Here we develop automated Piezoresponse Force Microscopy (PFM) for the exploration of combinatorial spread libraries and demonstrate its application in the SmxBi1-xFeO3 system with the ferroelectric-antiferroelectric morphotropic phase boundary. This approach relies on the synergy of the quantitative nature of PFM and the implementation of automated experiments that allow PFM-based sampling over macroscopic samples. The concentration dependence of pertinent ferroelectric parameters has been determined and used to develop the mathematical framework based on Ginzburg-Landau theory describing the evolution of these properties across the concentration space. We pose that a combination of automated scanning probe microscope and combinatorial spread library approach will emerge as an efficient research paradigm to close the characterization gap in the high-throughput materials discovery. We make the data sets open to the community and hope that this will stimulate other efforts to interpret and understand the physics of these systems.

Automated Microscopy, Combinatorial Library, Ferro↗