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Co(x)Ni(4-x)Sb(12-y)Sn(y) Ternary Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their high figure of merit, favorable mechanical properties, and good thermal stability. Binary skutterudites have received the majority of interest in recent years, as a result of successful double and triple filling schemes. Ternary skutterudites, such as Ni4Sb7Sn5, also demonstrate good thermoelectric performance, with high power factor and low thermal conductivity. Ternary skutterudites, as contrasted to binary systems, provide more possibility for tuning electronic structure as substitutions can be studied on three elements. The Co(x)Ni(4-x)Sb(12-y)Sn(y) system has been investigated as both a p- and n-type thermoelectric material, stable up to 200 C. The system is processed through a combination of solidification, mechanical alloying, and hot pressing steps. Rietveld structure refinement has revealed an interesting occupancy of Sn on both the 24g Wyckoff position with Sb as well as the 2a position as a rattler. In addition to thermoelectric properties, detailed processing routes have been investigated on the system.

Seebeck effect↗

Thermoelectric properties of Co(x)Ni(4-x)Sb(12-y)Sn(y) ternary skutterudites

Thermoelectric materials based on the skutterudite crystal structure have demonstrated enhanced performance (ZT greater than 1), along with good thermal stability and favorable mechanical properties. Binary skutterudites, with single and multiple fillers, have been intensively studied in recent years. Compared to binary skutterudites, the ternary systems have received less attention, e.g. Ni4Sb8Sn4. Ternary skutterudites are isoelectronic variants of binary skutterudites; cation substitutions appear to be isostructural to their binary analogues. In general, ternary skutterudites exhibit lower thermal conductivity. Ternary systems of Ni4Bi8Ge4, Ni4Sb8Ge4, and Ni4Sb8Sn4 were investigated using combined solidification and sintering steps. Skutterudite formation was not achieved in the Ni4Bi8Ge4 and Ni4Sb8Ge4 systems; skutterudite formation occurred in Ni4Sb8Sn4 system. P-type material was achieved by Co substitution for Ni. Thermoelectric properties were measured from 298 K to 673 K for Ni4Sb8Sn4, Ni4 Sb7Sn5 and Co2Ni2Sb7Sn5. N-type Ni4Sb8Sn4 exhibit the highest figure of merit of 0.1 at 523 K.

Seebeck Effect↗

Filled Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3 or CoAs3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) system has been investigated as both a p- and n-type thermoelectric material, and is stable up to 200 degrees Centigrade. Yb, Ce, and Dy fillers have been introduced into the skutterudite to study the influence of both the type and the quantity of fillers on processing conditions and thermoelectric properties. The system was processed through a multi-step technique that includes solidification, mechano-chemical alloying, and hot pressing which will be discussed along with thermoelectric transport properties.

Thermoelectricity↗

Central Elemental Abundance Ratios In the Perseus Cluster: Resonant Scattering or SN Ia Enrichment?

We have determined abundance ratios in the core of the Perseus Cluster for several elements. These ratios indicate a central dominance of Type 1a supernova (SN Ia) ejects similar to that found for A496, A2199 and A3571. Simultaneous analysis of ASCA spectra from SIS1, GIS2, and GIS3 shows that the ratio of Ni to Fe abundances is approx. 3.4 +/- 1.1 times solar within the central 4'. This ratio is consistent with (and more precise than) that observed in other clusters whose central regions are dominated by SN Ia ejecta. Such a large Ni overabundance is predicted by "convective deflagration" explosion models for SNe Ia such as W7 but is inconsistent with delayed detonation models. We note that with current instrumentation the Ni K(alpha) line is confused with Fe K(beta) and that the Ni overabundance we observe has been interpreted by others as an anomalously large ratio of Fe K(beta) to Fe K(alpha) caused by resonant scattering in the Fe K(alpha) line. We argue that a central enhancement of SN Ia ejecta and hence a high ratio of Ni to Fe abundances are naturally explained by scenarios that include the generation of chemical gradients by suppressed SN Ia winds or ram pressure stripping of cluster galaxies. It is not necessary to suppose that the intracluster gas is optically thick to resonant scattering of the Fe K(alpha) line.

Dupke, Renato A.↗

Characterizations of four specimens processed as a part of the M553 sphere forming experiment performed during the Skylab 1 and 2 flight

Four specimens identified as SL-1.3, SL-1.8, SL-1.9 and SL-2.5 were submitted for metallurgical characterization. These specimens had been processed in the M512 Facility as a part of the M553 Sphere Forming Experiment performed during the Skylab 1/2 flight. Three of these specimens, SL-1.3, SL-1.8, and SL-2.5 were designed to be melted completely by the electron beam and detach themselves from their support posts and resolidify while floating free in the near zero gravity and vacuum environment of space. Specimens SL-1.3 and SL-1.8 were completely melted, but it is believed they did not leave their posts before solidifying. Specimen SL-2.5 was only partially melted. Specimen SL-1.9 was to be completely melted and retained on a large sting which was accomplished as planned. The nominal composition of the four specimens was: (1) SL-1.3 - Ni 12% Sn; (2) SL-1.8 - Ni 30% Cu; (3) SL-1.9 - Pure Ni; and (4) SL-2.5 - Pure Ni. These four specimens have been examined according to the Phase B Characterization Plan. The results are discussed and compared with similar characterization analyses run on ground base specimens.

Hubbard, J. L.↗

Additional Trials & Tribulations in Synthesizing a Sulfide Standard

Well-characterized sulfide reference materials that can serve as matrix-matched calibrants for in-situ trace element analyses via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain elusive. Here, we describe the creation an in-house sulfide standard at NASA JSC that will be used to measure siderophile and chalcophile trace elements in low pressure experimental products, specifically pentlandite ([FeNi]9S8) and pyrrhotite ([FeNi]1-xS), as well as natural sulfides in terrestrial and meteoritic mineral assemblages. Recent methods in creating a homogenous sulfide standard include pressed pellets, synthesized chips, or fused glass [e.g. 1-3]. Other studies, however, have had success in forming homogenous FeS standards via synthesization methods [e.g. 4-6]. We present a variation of the method described in [4], in which we create a pyrrhotite standard doped with a variety of trace elements (Zn, As, Se, Mo, Ru, Rh, Pd, Sn, Sb, Te, W, Os, Ir, Pt, Au) at ~10-40 ppm and Cu at ~200 ppm. Sulfide compositions were constructed using Fe and Ni metal and elemental sulfur powders. Trace elements were added to elemental sulfur from Atomic Absorption Spectroscopy (AAS) elemental standards as either nitrate or chloride solutions to prevent oxidation of the metal powders. The dried sulfur mixture was mixed with Fe and Ni powders and mechanically mixed before two aliquots were placed in separate SiO2 tubes. Each tube was held under vacuum for ~30 minutes, sealed under vacuum, and then heated at 800C for 48 hours. Like [4], the synthesis products were composed of pourous sulfide crystals. Major element analyses of both experimental aliquots, collected using an Electron Probe Microanalyser (EPMA), yield indistinguishable major element compositions (uncertainties in 2SE & 2RSE[%]), with an average of 57.90  0.09 (0.16 %), 4.95  0.03 (0.55 %), and 39.70  0.14 (0.34 %), for Fe, Ni, and S, respectively. Trace element data were measured using a Photon Machines 193nm laser ablation system coupled to a Thermo-Scientific Element-XR ICP-MS. Spot sizes were limited to 50 μm due to the porous nature of the sulfide target material. Trace element abundances, normalized to Fe as an internal standard, were also found to be homogenous between the two aliquots, with weighted mean 2RSE (%) values of <3.0 for all trace elements. Synthesized products were re-powdered and absolute concentrations measured via solution ICP-MS. Although the sulfide appears to be homogenous, sintering experiments will be performed to more closely match the standard density to natural sulfides and minimize differences in ablation behavior. Improved density also allows for higher sensitivity (i.e. more compact target material) and larger spot sizes or traverses, as void space is eliminated. Additional major and trace element analyses on the products of the sintering experiments will be undertaken.

Jacob B Setera↗

Rapid solidification of levitation melted Ni-Sn alloy droplets with high undercooling

Experimental results obtained by high-speed optical temperature sensing for the rapid solidification of highly undercooled, levitation-melted Ni-Sn alloy droplets are presented. These data suggest a solidification model proceeding according to overlapping steps: (1) dendritic growth within the bulk undercooled melt, (2) continued recalescence as supersaturation of the interdendritic liquid dissipates, (3) fine-scale remelting within the dendrites, (4) ripening of the fine structure, and (5) solidification of remaining liquid at the end of recalescence.

Shiohara, Yuh↗

High-resolution mid-infrared spectra of Co II, Ni I, and Fe II in SN 1987A

Ground-based infrared observations of SN 1987A on day 612 after the explosion have yielded resolved line profiles of Co II, Ni I, Fe II at 10.52, 11.31, and 17.94 micron, respectively. The spectra were taken at a resolving power of about 1000 with an array grating spectrometer on the 4 m telescope of Cerro Tololo Inter-American Observatory. Based on the observed line intensities we have estimated the minimum mass of each ion: M(Co II) = (6.0 +/- 1.8) x 10 exp -5 solar mass; M(Ni I) = (1.1 +/- 0.1) x 10 exp -3 solar mass; and M(Fe II) = (8.0 +/- 1.5) x 10 exp -3 solar mass. From these we infer total masses for cobalt, nickel, and iron in the ejecta. The nickel and iron line profiles are markedly asymmetric. We interpret these as arising from two components, one centered on the stellar rest velocity with an approximately 3250 km/s full width, and the second at about +1200 km/s with an approximately 1100 km/s full width. The asymmetry may represent a large-scale fracturing of the ejecta by Rayleigh-Taylor instabilities.

Jennings, D. E.↗

Oxgen-burning hydrodynamics. 1: Steady shell burning

With new hydrodynamic techniques, the relatively fast evolutionary stages of a star prior to core collapse may be explicitly computed in two spatial dimensions, with a treatment of the microphysics (e.g., nuclear reactions, equation of state, neutrino cooling) which is comparable to typical one-dimensional simulations. The nature of shell oxygen burning in a massive star, prior to core collapse, is used as a first example; it is of particular interest because it is (1) the region in which Ni-56 will be produced by the supernova shock, (2) the region of the 'mass cut', which will separate the collapsed core from the ejected mantle, (3) the site of much of the explosive nucleosynthesis, and (4) a suggested source of symmetry breaking to drive mixing instabilities which were observed in SN 1987A. The nature of the shell burning affects the size of the core which will collapse. The method is illustrated on this test case, and the character of the convection is examined.

Arnett, David↗

The Double-Peaked SN 2013ge: A Type Ib/c Sn with an Asymmetric Mass Ejection or an Extended Progenitor Envelope

We present extensive multiwavelength (radio to X-ray) observations of the Type Ib/c supernova (SN Ib c) SN 2013ge from -13 to +457 days relative to maximum light, including a series of optical spectra and Swift UV-optical photometry beginning 2-4 days post-explosion. This data set makes SN 2013ge one of the best-observed normal SNe Ib/c at early times-when the light curve is particularly sensitive to the progenitor configuration and mixing of radioactive elements -and reveals two distinct light curve components in the UV bands. The first component rises over 4-5 days and is visible for the first week post-explosion. Spectra of the first component have blue continua and show a plethora of moderately high velocity (approximately 15,000 km/s) but narrow (approximately 3500 km/s)spectroscopic features, indicating that the line-forming region is restricted. The explosion parameters estimated for the bulk explosion (M(sub ej) approximately 23 solar mass; E(subK) approximately (1-2) x 10(exp 51) erg) are standard for SNe Ib/c, and there is evidence forweak He features at early times-in an object that would have otherwise been classified as Type Ic. In addition,SN 2013ge exploded in a low-metallicity environment (approximately 0.5 atomic mass), and we have obtained some of the deepest radio and X-ray limits for an SN Ib/c to date, which constrain the progenitor mass-loss rate to be M less than 4 x 10(exp -6) solar mass/yr. We are left with two distinct progenitor scenarios for SN 2013ge, depending on our interpretation of the early emission. If the first component is cooling envelope emission, then the progenitor of SN 2013ge either possessed an extended (greater than or approximately 30 solar radius) envelope or ejected a portion of its envelope in the final less than or approximately 1 yr before core collapse. Alternatively, if the first component is due to outwardly mixed Ni-56, then our observations are consistent with the asymmetric ejection of a distinct clump of nickel-rich material at high velocities. Current models for the collision of an SN shock with a binary companion cannot reproduce both the timescale and luminosity of the early emission in SN 2013ge. Finally, the spectra of the first component of SN 2013ge are similar to those of the rapidly declining SN 2002bj.

supernovae: general – supernovae: individual (SN↗

Multi-Anvil Experimentation Applied to Planetary Differentiation

Planets undergo differentiation that includes segregation of metal from silicate at high temperatures and pressures ranging from deep planetary core pressures (>300 GPa for Earth)to very shallow conditions of asteroids (<100 MPa).The multi-anvil solid media apparatus accesses the middle part of this range from 3 to 30 GPa –pressure relevant to the interior of Mercury, Venus, Earth, Earth’s Moon, and Mars. Early planets are thought to have experienced high temperatures from a combination of heat sources including radioactive decay, gravitational and accretional heating, and impact processes. These heating events led to melting of mantles and cores, thus requiring an understanding of solid-liquid equilibria in metal-silicate systems. In 2006 we established a multi-anvil facility at NASA-JSC combining an 880 ton press and a Kawai/Walker type module from Rockland Research. Our high PT work has been greatly facilitated by use of the COMPRES multi-anvil assemblies (1). Our recent work has included studies of element partitioning between liquid metal and liquid silicate(e.g., 2), as well as between minerals and melts(e.g., 3), both of which have led to better constraints on the timing and conditions of planetary differentiation(e.g. 4). Several examples involving sustained efforts will be summarized below and for the presentation. The distribution of siderophile (iron-loving) elements between core and mantle is controlled by metal-silicate equilibrium across a wide range of pressures. Therefore, experimentation across this pressure range helps to calibrate elemental partitioning models that can be applied to planets, and used to predict mantle chemistry and composition during planetary differentiation. Our studies have focused on a wide range of siderophile elements (refractory Ni, Co, W, Mo; volatile P, Ga, Cu, Sn, Sb; highly siderophile Au, Pd) that have constrained partitioning, valence, and isotopic fractionation, and applied to Earth, Moon, and Mars. When molten mantles (magma oceans) cool enough to initiate crystallization, the solids precipitate at depth and in large planets this involves high pressure phases like garnet, majorite, akimotoite, and ringwoodite. As these solids precipitate they can segregate from liquid by density contrasts, thus causing elemental fractionation which can be used to decipher timing of differentiation. Mineral/melt and metal/silicate equilibria in our lab have helped to better understand high pressure fractionation of isotopic parent/daughter pairs Hf/W, Mn/Cr, Pd/Ag, Pt/Os, Re/Os, and U/Pb, and their application to Earth, Moon and Mars. There remains great potential for multi-anvil experimentation to shed light on many pressure–dependent aspects of planetary evolution such as core formation, high pressure phase equilibria, redox equilibria, and volatile evolution and storage. References1. Leinenweber, K., et al.(2012) American Mineralogist,97, 353–368. 2.Righter, K., et al.(2020) Geochem. Persp. Lett.15, 1-6.3. Righter, K., et al.(2020) Met. Planet. Sci 55, 2741-2757.4. Righter, K., et al.(2020)Earth and Planetary Science Letters,552, 116590.

pressure↗

Day 640 infrared line and continuum measurements: Dust formation in SN 1987A

We have measured day 640-645 line and continuum spectra of (Ni II) 6.6 micrometer (Ne II) 12.8 micrometer (line emission was not detected), and (Fe II) 17.9 and 26.0 micrometer from SN 1987A. The high velocity feature at v(sub HVF) approximately 3900 km/sec found in both of our day 410 (Fe II) spectra is again detected in the day 640 (Ni II) spectrum, although the signal-to-noise of the day 640 (Fe II) spectra is insufficient to show this feature. The continuum fluxes provide clear evidence for the formation of dust between day 410 and day 640 and are best fitted by a graybody spectrum with a temperature of 342 +/- 17 K at day 640 and a surface area corresponding to a minimum dust velocity v(sub dust) = 1910 +/- 170 km/sec. Optically thin dust emissivity laws proportional to lambda(exp -1) or lambda(exp -2) are inconsistent with the data. Either the dust grains are large (radius a much greater than 4 micrometer and radiate like individual blackbodies, or else they are located in clumps optically thick in the 6-26 micrometer range. The (Ni II) 6.6 micrometer line flux yields a minimum Ni(+) mass of 5.8 +/- 1.6 x 10(exp -4) solar mass and a Ni/Fe abundance ratio of 0.06 +/- 0.02, equal to the solar value. The ratio of the two (Fe II) line profiles implies a gas temperature 2600 +/- 700 K, a drop of 1800 +/- 800 K from our day 410 measurement. The (Fe II) 26.0 micrometer line flux has decreased by a factor of 2 and the day 640 (Ni II) profile is blueshifted by -440 +/- 270 km/sec, relative to observations before day 500. We show that the decrease in the (Fe II) flux and the blueshift are not produced by a decrease in electron scattering optical depth, electron density, or temperature, but rather are probably due to obscuration by the same dust which produces the infrared continuum. This supports the interpretation that the dust spectrum is produced by optically thick clumps. We discuss possible explanations for the discrepancy between the mass of Fe(+) detected and the total iron mass required to power the light curve. The decrease in the (Fe II) fluxes relative to the decrease required to account for the blueshifts of optical lines from non-iron-group elements and the similarity between v(sub dust) and the Ni(+) expansion velocity imply a spatial association between the dust clumps and the iron-group elements. In addition, the larger blueshift observed for the near and far-infrared, heavy metal transitions relative to non-iron-group lines suggests that the iron-group elements are somewhat segregated from lighter elements such as the Mg(sup 0) and O(sup 0) responsible for shorter wavelength lines. We speculate that FeS may be an important constituent of the dust. A comparison of our line profiles with radiative transfer models shows that while power law and exponential density distributions yield reasonable fits to the data, polytrope distributions provided significantly worse agreement. The best fits require a substantial fraction of the iron to be undetectable, and are consistent with maximum expansion velocities of v(sub max) approximately 3000 km/sec.

Colgan, Sean W. J.↗

SN 2010ay is a Luminous and Broad-lined Type Ic Supernova within a Low-metallicity Host Galaxy

We report on our serendipitous pre-discovery detection and detailed follow-up of the broad-lined Type Ic supernova SN2010ay at z approx 0.067 imaged by the Pan-STARRS1 3pi survey just approx 4 days after explosion. Combining our photometric observations with those available in the literature, we estimate the explosion date and the peak luminosity of the SN, M(sub R) approximately equals 20.2 mag, significantly brighter than known GRB-SNe and one of the most luminous SNe Ibc ever discovered. We measure the photospheric expansion velocity of the explosion from our spectroscopic follow-up observations, v(sub ph) approximately equals 19.2 X 10 (exp 3) km/s at approx 40 days after explosion. In comparison with other broad-lined SNe, the characteristic velocity of SN2010ay is 2 - 5 X higher and similar to the measurements for GRB-SNe at comparable epochs. Moreover the velocity declines two times slower than other SNe Ic-BL and GRB-SNe. Assuming that the optical emission is powered by radioactive decay, the peak magnitude implies the synthesis of an unusually large mass of Ni-56, M(sub Ni) = 0.9(+0.1/-0.1) solar mass. Our modeling of the light-curve points to a total ejecta mass, M(sub ej) approx 4.7 Solar Mass, and total kinetic energy, E(sub K,51) approximately equals 11. Thus the ratio of M(sub Ni) to M(sub ej) is at least twice as large for SN2010ay than in GRB-SNe and may indicate an additional energy reservoir. We also measure the metallicity (log(O/H) + 12 = 8.19) of the explosion site within the host galaxy using a high S/N optical spectrum. Our abundance measurement places this SN in the low-metallicity regime populated by GRB-SNe, and approx 0.2(0.5) dex lower than that typically measured for the host environments of normal (broad-lined) Ic supernovae. Despite striking similarities to the recent GRB-SN100316D/2010bh, we show that gamma-ray observations rule out an associated GRB with E(sub gamma) approx < 6 X 10(exp 48) erg (25-150 keV). Similarly, our deep radio follow-up observations with the Expanded Very Large Array rule out relativistic ejecta with energy, E approx > 10(exp 48) erg. These observations challenge the importance of progenitor metallicity for the production of a GRB, and suggest that other parameters also play a key role.

Sanders, N. E.↗

SN 1993J: A Type IIb supernova

The evolution of the bright Type II supernova discovered last year in M81, SN 1993J, is consistent with that expected for the explosion of a star which on the main sequence had a mass of 13-16 Solar Mass but which, owing to mass exchange with a binary companion (a intially approximately 3-5 AU, depending upon the actual presupernova radius and the masses of the two stars) lost almost all of its hydrogen-rich envelope during late helium burning. At the time of explosion, the helium core mass was 4.0 +/- 0.5 Solar Mass and the hydrogen envelope, 0.20 +/- 0.05 Solar Mass. The envelope was helium and nitrogen-rich (carbon-deficient) and the radius of the star, 4 +/- 1 x 10(exp 13) cm. The luminosity of the presupernova star was 3 + 1 x 10(exp 38) ergs/s, with the companion star contributing an additional approximately 10(exp 38) ergs/s. The star may have been a pulsating variable at the time of the explosion. For an explosion energy near 10(exp 51) ergs (KE at infinity) and an assumed distance of 3.3 Mpc, a mass of Ni-56 in the range 0.07 +/- 0.01 Solar Mass was produced and ejected. This presciption gives a light curve which compares favorably with the bolomatric observations. Color photometry is more restrictive and requires a model in which the hydrogen-envelope mass is low and the mixing of hydrogen inward has been small, but in which appreciable Ni-56 has been mixed outward into the helium and heavy-element core. It is possible to obtain good agreement with B and V light curves during the first 50 days, but later photometry, especially in bands other than B and V, will require a non-local thermo-dynamic equilibrium (LTE) spectral calculation for comparison. Based upon our model, we predict a flux of approximately 10(exp -5)(3.3 Mpc/D)(exp 2) photons/sq cm/s in the 847 keV line of CO-56 at peak during 1993 August. It may be easier to detect the Computonized continuum which peaks at a few times 10(exp -4) photons /s/sq cm/MeV at 40 keV a few months after the explosion (though neither of these signals were, or should have been, detected by the Compton Gamma-Ray observatory (CGRO). The presupernova star was filing its Roche lobe at the time of the explosion and thus its envelope was highly deformed (about 3:2). The companion star is presently embedded in the supernova, but should becopme visable at age 3 yr (perhaps earlier in the ultraviolet) when the supernova has faded below 10(exp 38) ergs/s. Indeed, if 'kicks' have not played an important role, it is still bound to the neutron star.

Woosley, S. E.↗