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Synthesis Of Ir(1-x-y)Rh(x)Co(y)Sb(3) Semiconductors

Ir(1-x-y)Rh(x)Co(y)Sb(3) semiconductors synthesized by gradient-freeze and sintering techniques. Sintering techniques used for variety of compositions; gradient-freeze technique used for RhSb(3) and CoSb(3).

Caillat, Thierry↗

Skutterudites: a New Class of Promising Thermoelectric Materials

Based on literature data and experimental findings at JPL, semiconductors with the skutterudite structure TPn(sub 3) (where T is a transition metal element such as Co, Rh, Ir, Ni and Pd, and Pn is a pnicogen element such as P, As and Sb) possess attractive characteristics and show a good potential for high ZT values. the high degree of covalency results in high mobility and low electrical resistivity values while a relatively complex 32-atom unit cell results in a reasonably low thermal conductivity.

skutterudites thermoelectric material↗

Semiconductor apparatus utilizing gradient freeze and liquid-solid techniques

Transition metals of Group VIII (Co, Rh and Ir) have been prepared as semiconductor compounds with the general formula TSb.sub.3. The skutterudite-type crystal lattice structure of these semiconductor compounds and their enhanced thermoelectric properties results in semiconductor materials which may be used in the fabrication of thermoelectric elements to substantially improve the efficiency of the resulting thermoelectric device. Semiconductor materials having the desired skutterudite-type crystal lattice structure may be prepared in accordance with the present invention by using vertical gradient freezing techniques and/or liquid phase sintering techniques. Measurements of electrical and thermal transport properties of selected semiconductor materials prepared in accordance with the present invention, demonstrated high Hall mobilities (up to 1200 cm.sup.2.V.sup.-1.s.sup.-1) and good Seebeck coefficients (up to 150 .mu.VK.sup.-1 between 300.degree. C. and 700.degree. C.). Optimizing the transport properties of semiconductor materials prepared from elemental mixtures Co, Rh, Ir and Sb resulted in a substantial increase in the thermoelectric figure of merit (ZT) at temperatures as high as 400.degree. C. for thermoelectric elements fabricated from such semiconductor materials.

Fleurial, Jean-Pierre↗

Development of Primary Volatile Production in COMET C/20O9 Pl (GARRADD) During its 2011-2O12 Apparition

We quantified primary volatiles in comet C/2009 Pl (Garradd) through pre- and post-perihelion observations acquired during its apparition in 2011-12 [1,2,3]. Detected volatiles include H2O, CO, CH4, C2H2, C2H6, HCN, NH3, H2CO, and CH3OH. We present production rates and chemical abundance ratios (relative to water) for all species, and I-D spatial profiles for multiple primary volatiles. We discuss these findings in the context of an emerging taxonomy based on primary volatiles in comets [4]. We used three spectrometer/telescope combinations. On UT 20ll August 7 (Rh 2.4 AU) and September 17-21 (Rh 2.0 AU), we used CRIRES at ESO's Very Large Telescope (VLT) [1]. On September 8 and 9 (Rh 2.1 AU), we used NIRSPEC at Keck-2 and CSHELL at IRTF [2]. Using NIRSPEC on October 13 and 2012 January 08 (Rh 1.83 and 1.57 AU, respectively), we detected nine primary volatiles pre-perihelion, and six post-perihelion [3]. CO was enriched in Garradd while C2H2 was strongly depleted. C2H6 and CH3OH displayed abundances close to those measured for the majority of Oort cloud comets observed to date. The high fractional abundance of CO identifies comet C12009 P1 as a CO-rich comet. Spatial profiles revealed notable differences among individual primary species. Given the relatively large heliocentric distance of C/2009 Pl, we explored the effect of water not being fully sublimated within our field of view and we identi$, the "missing" water fraction needed to reconcile the retrieved abundance ratios with the mean values found for "organics-normal" comets.

Mumma, M. J.↗

High performance thermoelectric materials and methods of preparation

Transition metals (T) of Group VIII (Co, Rh and Ir) have been prepared as semiconductor alloys with Sb having the general formula TSb.sub.3. The skutterudite-type crystal lattice structure of these semiconductor alloys and their enhanced thermoelectric properties results in semiconductor materials which may be used in the fabrication of thermoelectric elements to substantially improve the efficiency of the resulting thermoelectric device. Semiconductor alloys having the desired skutterudite-type crystal lattice structure may be prepared in accordance with the present invention by using vertical gradient freeze techniques, liquid-solid phase sintering techniques, low temperature powder sintering and/or hot-pressing. Measurements of electrical and thermal transport properties of selected semiconductor materials prepared in accordance with the present invention, demonstrated high Hall mobilities (up to 8000 cm.sup.2.V.sup.-1.s.sup.-1), good Seebeck coefficients (up to 400 .mu.VK.sup.-1 between 300.degree. C. and 700.degree. C.), and low thermal conductivities (as low as 15 mW/cmK). Optimizing the transport properties of semiconductor materials prepared from elemental mixtures Co, Rh, Ir and Sb resulted in a two fold increase in the thermoelectric figure of merit (ZT) at temperatures as high as 400.degree. C. for thermoelectric elements fabricated from such semiconductor materials.

Fleurial, Jean-Pierre↗

Beyond 3 Au from the Sun: the Hypervolatiles CH4, C2H6, and CO in the Distant Comet C2006 W3 (Christensen)

Comet C/2006 W3 (Christensen) remained outside a heliocentric distance (Rh) of 3.1 au throughout its apparition, but it presented an exceptional opportunity to directly sense a suite of molecules released from its nucleus. The Cryogenic Infrared Echelle Spectrograph at ESO-VLT detected infrared emissions from the three hypervolatiles (CO, CH4, and C2H6) that have the lowest sublimation temperatures among species that are commonly studied in comets by remote sensing. Even at Rh 3.25 au, the production rate of each molecule exceeded those measured for the same species in a number of other comets, although these comets were observed much closer to the Sun. Detections of CO at Rh = 3.25, 4.03, and 4.73 au constrained its post-perihelion decrease in production rate, which most likely dominated the outgassing. At 3.25 au, our measured abundances scaled as CO/CH4/C2H6 approx. = 100/4.4/2.1. The C2H6/CH4 ratio falls within the range of previously studied comets at Rh < 2 au, while CO/CH4 is comparatively high and similar to in situ measurements from Rosetta at approx.10 km from the nucleus of 67P/Churyumov-Gerasimenko conducted at a very similar Rh (3.15 au). The independent detections of H2O (Herschel Space Observatory) and CO (this work) imply a coma abundance H2O/CO approx. = 20% in C/2006 W3 near Rh = 5 au. All these measurements are of high value for constraining models of nucleus sublimation (plausibly CO-driven) beyond Rh = 3au, where molecular detections in comets are still especially sparse.

Bonev, Boncho P.↗

LA-ICP-MS Study of Trace Elements in the Chanuskij Metal

This progress report covers work done during the second year of the 3-year proposal. During this year we resolved many issues relevant to the analytical technique developed by us for measuring trace elements in meteoritic metals. This technique was used to measure concentrations of Fe, Ni, Co, Cr, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sb, W, Re, Os, Ir, Pt, and Au in eight large (120 - 160 microns) metal grains from both "igneous" and "metamorphic" lithologies of the Chanuskij silicate inclusions. The first application of OUT technique to metal grains from thin sections showed some limitations. Small thickness of metal grains in the thin section limited the signal to 3-4 time-slices instead of 10- 1 1 ones in polished sections of iron meteorites studied before.

Petaev, Michail I.↗

Regolith Volatile Characterization (RVC) in RESOLVE

Resource investigation in the lunar poles is of importance to the potential impact of in-situ resource utilization (ISRU). The RESOLVE project developed a payload to investigate the permanently shadowed areas of the lunar poles and demonstrate ISRU technology. As a part of the RESOLVE project, the regolith volatile characterization (RVC) subsystem was designed to examine the release of volatiles from sample cores. The test sample was heated in the reactor to release the volatiles where they were analyzed with gas chromatography. Subsequently, the volatile sample was introduced into the lunar water resource demonstration (LWRD) subsystem where the released hydrogen and water were selectively captured. The objective of the Regolith Volatile Characterization (RVC) subsystem was to heat the crushed core sample and determine the desorption of volatile species of interest. The RVC subsystem encompasses the reactor and the system for volatile analysis. The system was designed to analyze H2, He, CO, CO2, N2, 02, CH4, H2S and H2O. The GC chosen for this work is a Siemens MicroSAM process GC with 3 columns and 8 TCD detectors. Neon was chosen as the carrier gas to enhance the analysis of hydrogen and helium.The limit of detection for the gases is approx.1000ppm for H2, CO. CO2 , N2, O2 and H2 S. The limit of detection for CH4 is approx.4000ppm and the water limit of detection is -10000 ppm with a sample analysis time of 2-3 minutes. These values (with the exception of water and H2S) were determined by dilution of a six gas mixture from Scott Gas (5% CO2, CO, O2, N2, 4% CH4 and H2) using mass flow controllers (MFC5). Water was calibrated at low levels using an in house relative humidity (RH) generator. H 2S and high concentrations of H2 were calibrated by diluting a pure stream of gas with MFCs. Higher concentrations of N2 and 02 were calibrated using Air again diluting with MFCs. There were three modification goals for the GC in EBU2 that would allow this process GC to be used in the field demo for RESOLVE. The first modification was to decrease the weight associated with the GC, this included eliminating the explosion proof case (Figure 1) and replacing it with a lightweight case as well as using an on board COPV tank for the neon carrier gas. The next goal was to add a second oven for the molecular sieve column to allow for dual temperature control during GC operation; the separation of hydrogen and helium is optimum at lower temperatures while the water analysis required higher temperatures creating a competing design requirement. The second oven also allows a lower limit of detection for water quantification and avoids the possibility of water condensing in the GC which could ruin the column characteristics. The final goal was to modify the column arrangement to optimize the system for our specific application. Figure 2 shows the internal details of the module optimized optimized for our field application. The modifications and performance of the gas analysis system will be discussed in detail.

Captain, Janine↗