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All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Hydrogenation of butanal over silica-supported Shvo’s catalyst and its use for the gas-phase conversion of propene to butanol via tandem hydroformylation and hydrogenation

The objective of the present study was to develop a heterogeneous catalyst for the hydrogenation of butanal that could function in the presence of CO and propene and, hence, could be used in a tandem reactor to enable the gas-phase conversion of propene and synthesis gas to butanol. To this end, we investigated the activity of silica-supported Shvo's catalyst (Shvo/SiO 2 ) for the gas-phase hydrogenation of butanal. Experiments were performed to determine the kinetics of n- and iso-butanal hydrogenation. The apparent activation energies and the apparent partial pressure dependencies of n - and iso-butanal, H 2 , and CO on the rates of n- and iso-butanol formation were determined. A mechanism for butanal hydrogenation was proposed to rationalize the observed kinetics and some of the reaction intermediates were observed by in situ infrared and 31 P MAS NMR spectroscopy. It was found that Shvo/SiO 2 was inhibited by SX (SX = sulfoxanthphos) and CO, and is inactive for alkene hydrogenation. The tandem catalytic conversion of propene and synthesis gas to butanol was then carried out using a SX-Rh supported ionic liquid phase (SILP) catalyst to promote the hydroformylation of propene to butanal and Shvo/SiO 2 to promote the hydrogenation of butanal to butanol. The rate expressions describing the kinetics of each of the catalysts were then used to predict operating conditions required to achieve high conversion of propene to butanol. Under the most favorable conditions examined (H 2 /CO = 10), an overall yield of 13% to butanol was achieved with 15% propene conversion and 90% aldehyde conversion at a temperature of 413 K.

Butanal↗
DOE OSTI2026

Lunar accelerometer network gravitational observatory (LANGO)

With ground-based interferometers detecting hundreds of gravitational-wave (GW) events, GW astronomy has continued to blossom. U.S. and European scientists are developing plans to construct third-generation ground-based interferometers. ESA has proceeded through the mission formulation phase of space-based interferometer in a lower-frequency band, 10 –4 –0.1 Hz. Despite all these exciting developments, there is still a missing frequency band, 0.1–10 Hz. This mid-frequency band is rich with interesting astrophysical events. Coalescence and merger of intermediate-mass black holes (IMBHs) will occur in this frequency band. Coalescing stellar-mass BHs will pass through this frequency band days before they reach the frequency band of LIGO and Virgo. Detection of such signals would enable a mid-frequency detector to issue an advance notice to the high-frequency GW detectors, as well as to optical, x-ray and γ-ray telescopes. We propose Lunar Accelerometer Network Gravitational Observatory (LANGO) to detect GWs in this frequency band. In the first phase (LANGO 1), we propose to deploy four ambient-temperature (250 K) accelerometers in the tetrahedral or in a square configuration on the hemisphere facing the Earth. After successful operation at 250 K, LANGO would be upgraded to a cryogenic (4 K) version with over two orders of magnitude increased sensitivity (LANGO 2), with coherent rejection of seismic noise implemented. LANGO is a full-tensor detector, capable of determining the source direction and wave polarization. Each test mass (TM) is suspended as a pendulum with resonance frequency ∼ 0.01 Hz, thus is only weakly coupled to the lunar surface horizontally. LANGO is designed to detect the relative motion of globally separated, nearly free, TMs by using the Moon as a large quiet platform. LANGO 1 and 2 accelerometers aim at sensitivities ⩽ 10 –11 m s –2 Hz –1/2 and ⩽ 10 –13 m s –2 Hz –1/2 in the horizontal axes over the frequency band of 1 mHz–10 Hz, which yield GW sensitivities 1.1 x 10 -21 Hz -1/2 and 3.8 x 10 -24 Hz -1/2 at 1 Hz, respectively. The LANGO accelerometers will be 10 3 –10 5 times more sensitive than Apollo seismometers. With such sensitivity, LANGO will also make great contribution to the advancement of lunar geophysics.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Microstructure, compression properties, and oxidation behavior of Hf-25Ta-5Me alloys (Me is Mo, Nb, W, 0.5Mo + 0.5 W, Cr, or Zr)

Hf–Ta based alloys have recently been investigated as potential candidates for high-temperature structural applications. While most attentions have been given to the properties above ~1200 °C where the alloys are mainly single-phase BCC structures and have excellent oxidation performance due to formation of super-oxides, structural properties at lower temperatures are equally important for applications in which an alloy may experience a range of temperatures. In the present work, microstructure, phase composition, mechanical properties and oxidation behavior of six Hf-25Ta-5Me alloys (Me is Mo (HTM alloy), W (HTW), 0.5Mo + 0.5 W (HTMW), Cr (HTC) or Zr (HTZ), the compositions are in at.%) are reported at temperatures below the eutectoid transformation. The alloys were prepared by arc melting followed by hot isostatic pressing for 3 h at 1400 °C and 207 MPa. All the alloys display coarse grains of partially or fully transformed (by a eutectoid reaction) high-temperature BCC phase. The eutectoid regions consist of fine lamellae of Hf-rich HCP and Ta-rich BCC phases. The ternary alloys containing W or Cr also contained small amounts of a cubic Laves phase. At 25 °C, the HTW alloy was the strongest (yield stress σ y = 1966 MPa) but brittle and HTZ was the weakest (σ y = 1120 MPa) but ductile among the studied alloys. Other alloys showed intermediate behaviors. In general, the room temperature ductility of the alloys increased with decreasing σy. All alloys maintained high strength up to 800 °C, but displayed a noticeable strength decrease at 1000 °C. At 1000 °C, HTMW was the strongest alloy (σ y = 468 MPa) and HTC was the weakest alloy (σ y = 368 MPa). All alloys had excellent deformability at 1000 °C. Oxidation behavior of the alloys was studied at 800 °C and 1000 °C and compared with that of Hf–27Ta binary alloy. Although the ternary additions improved oxidation resistance, overall oxidation performance of the studied alloys at 800 °C and 1000 °C was poor.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Low-temperature Phase and Morphology Transformations in Noble Metal Nanocatalysts

In situ real-time x-ray diffraction was used to study temperature-induced structural changes of 1-5 nm Au, Pt, and AuPt nanocatalysts supported on silicon substrates. Synchrotron-based x-ray diffraction indicates that the as-synthesized Au and Au{sub 64}Pt{sub 36} nanoparticles have a non-crystalline structure, while the Pt nanoparticles have the expected cubic structure. The nanoparticles undergo dramatic structural changes at temperatures as low as 120 C. During low-temperature annealing, the Au and AuPt nanoparticles first melt and then immediately coalesce to form 4-5 nm crystalline structures. The Pt nanoparticles also aggregate but with limited intermediate melting. The detailed mechanisms of nucleation and growth, though, are quite different for the three types of nanoparticles. Most interestingly, solidification of high-density AuPt nanoparticles involves an unusual transient morphological transformation that affects only the surface of the particles. AuPt nanoparticles on silicon undergo partial phase segregation only upon annealing at extremely high temperatures (800 C).

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Seebeck and Figure of Merit Enhancement by Rare Earth Doping in Yb14-xRExZnSb11 (x = 0.5)

Yb14ZnSb11 has been of interest for its intermediate valency and possible Kondo designation. It is one of the few transition metal compounds of the Ca14AlSb11 structure type that show metallic behavior. While the solid solution of Yb14Mn1-xZnxSb11 shows an improvement in the high temperature figure of merit of about 10% over Yb14MnSb11, there has been no investigation of optimization of the Zn containing phase. In an effort to expand the possible high temperature p-type thermoelectric materials with this structure type, the rare earth (RE) containing solid solution Yb14-xRExZnSb11 (RE = Y, La) was investigated. The substitution of a small amount of 3+ rare earth (RE) for Yb2+ was employed as a means of optimizing Yb14MnSb11 for use as a thermoelectric material. Yb14ZnSb11 is considered an intermediate valence Kondo system where some percentage of the Yb is formally 3+ and undergoes a reduction to 2+ at ~85 K. The substitution of a 3+ RE element could either replace the Yb3+ or add to the total amount of 3+ RE and provides changes to the electronic states. RE = Y, La were chosen as they represent the two extremes in size as substitutions for Yb: a similar and much larger size RE, respectively, compared with Yb3+. The composition x = 0.5 was chosen as that is the typical amount of RE element that can be substituted into Yb14MnSb11. These two new RE containing compositions show a significant improvement in Seebeck while decreasing thermal conductivity. The addition of RE increases the melting point of Yb14ZnSb11 so that the transport data from 300 K to 1275 K can be collected. The figure of merit is increased five times over that of Yb14ZnSb11 and provides a zT ~0.7 at 1275 K.

Kunz Wille, Elizabeth L. (ORCID:0000000228062663)↗
DOE OSTI2020

Phase Change-Driven Negative Activation Energies in Pd/Carbon-Based/Organic Getter Hydrogenation Reactions

In this study, the hydrogenation of 1,4-diphenylbutadiyne (DPB) blended with carbon-supported Pd (DPB–Pd/C) in the form of pellets was investigated by isothermal–isobaric experiments at 1333 Pa of H 2 and in the temperature range of 291–315 K. The extracted kinetics were then used in conjunction with a complementary constant rate of H 2 input experimentation to model the performance of a DPB-catalysis/support system as a function of temperature and H 2 partial pressure. First-principles density functional theory (DFT) calculations were also performed to shed light on the molecular level energetics of DPB and its intermediate states. A seemingly puzzling formation of alternate positive activation energy barrier (higher reaction rate with higher temperature) and negative activation energy barrier (higher reaction rate with lower temperature) zones during the hydrogenation process was discovered. However, this observed phenomenon can be logically explained in terms of the associated phase changes and H 2 transport in the material. This work provides a good illustration of a rarely encountered chemical process with a negative activation energy barrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Triple conducting cathode material for intermediate temperature protonic ceramic electrochemical devices

The present invention relates to a protonic ceramic fuel cell, a cathode for a protonic ceramic fuel cell, and a method of making the same. More specifically, the cathode for a protonic ceramic fuel cell utilizes a phase-pure perovskite structure of the compound BaCo 0.4 Fe 0.4 Zr 0.2-x Y x O 3- delta., where x is between about 0 and about 0.2. The cathode material may then be utilized in a PCFC as either a thin film porous cathode or as nanoparticles infiltrated into a cathode bone having a different structure.

Tong, Jianhua↗
DOE OSTI2020

Polysulfide reduction and Li 2 S phase formation in the presence of lithium metal and solid electrolyte interphase layer

Lithium sulfur battery is an attractive next generation technology that can meet many demands of modern society. Unfortunately, the lithium sulfur battery faces unique issues related to the polysulfide shuttle effect, that is due to reduction products dissolving in the electrolyte and their subsequent reduction on the lithium metal electrode. This adds further problems to the already challenging needs of understanding and engineering a solid electrolyte interphase (SEI) layer with desired properties. One of the most important SEI properties is its passivation of lithium metal which is critically important to the overall battery performance. Passivation is difficult to measure experimentally without the influence of many factors. This study reports an investigation of the reduction of the intermediate Li 2 S 8 over lithium already passivated with Li 2 O, Li 2 CO 3 , LiOH, LiF and Li 2 S along with exploration of Li 2 S 8 reduction over pristine lithium nanoclusters using first principles computational models. Significant formation of Li 2 S phase nucleation is found to stabilize the reduction products of the Li 2 S 8 . Here, the formation of Li 2 S is explored in-depth with lithium nanocluster-based models determining a 2 V potential increase for the reduction of polysulfides due to the formation of Li 2 S. This investigation demonstrates passivation effects of important SEI components including Li 2 S.

25 ENERGY STORAGE↗
DOE OSTI2021

Ultraviolet photodissociation of gas-phase iron pentacarbonyl probed with ultrafast infrared spectroscopy

It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. Here we employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO) 3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Study on the Microstructure, Mechanical Properties and Corrosion Behavior of Mg-Zn-Ca Alloy Wire for Biomaterial Application

Due to their excellent biocompatibility and biodegradability, magnesium alloy wires have attracted much attention for biomaterial applications including orthopedic K-wires and sutures in wound closure. In this study, Mg-3Zn-0.2Ca alloy wires were prepared by cold drawing combined with proper intermediate annealing process. Microstructures, texture, mechanical properties and corrosion behavior of Mg-3Zn-0.2Ca alloy wire in a simulated body fluid were investigated. The results showed that the secondary phase and average grain size of the Mg-3Zn-0.2Ca alloy were refined in comparison with the as-extruded alloy and a strong (0002)<10-10>//DD basal fiber texture system was formed after multi-pass cold drawing. After the annealing, most of the basal planes were tilted to the drawing direction (DD) by about 35°, presenting the characteristics of random texture, and the texture intensity decreased. The as-annealed wire shows good mechanical properties with the ultimate tensile strength (UTS), yield strength (YS) and elongation of 253 ± 8.5 MPa, 212 ± 11.3 MPa and 9.2 ± 0.9%, respectively. Electrochemical and hydrogen evolution measurements showed that the corrosion resistance of the Mg-3Zn-0.2Ca alloy wire was improved after the annealing. The immersion test indicated that the Mg-3Zn-0.2Ca wire exhibited uniform corrosion behavior during the initial period of immersion, but then exhibited local corrosion behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Photodissociative Cross-Linking of Non-covalent Peptide-Peptide Ion Complexes in the Gas Phase

We report a gas-phase UV photodissociation study investigating non-covalent interactions between neutral hydrophobic pentapeptides and peptide ions incorporating a diazirine-tagged photoleucine residue. Phenylalanine (Phe) and proline (Pro) were chosen as the conformation-affecting residues that were incorporated into a small library of neutral pentapeptides. Gas-phase ion-molecule complexes of these peptides with photo-labeled pentapeptides were subjected to photodissociation. Selective photocleavage of the diazirine ring at 355 nm formed short-lived carbene intermediates that underwent cross-linking by insertion into H–X bonds of the target peptide. The cross-link positions were established from collision-induced dissociation tandem mass spectra (CID-MS{sup 3}) providing sequence information on the covalent adducts. Effects of the amino acid residue (Pro or Phe) and its position in the target peptide sequence were evaluated. For proline-containing peptides, interactions resulting in covalent cross-links in these complexes became more prominent as proline was moved towards the C-terminus of the target peptide sequence. The photocross-linking yields of phenylalanine-containing peptides depended on the position of both phenylalanine and photoleucine. Density functional theory calculations were used to assign structures of low-energy conformers of the (GLPMG + GLL*LK + H){sup +} complex. Born-Oppenheimer molecular dynamics trajectory calculations were used to capture the thermal motion in the complexes within 100 ps and determine close contacts between the incipient carbene and the H–X bonds in the target peptide. This provided atomic-level resolution of potential cross-links that aided spectra interpretation and was in agreement with experimental data. .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Autoignition behavior of gasoline/ethanol blends at engine-relevant conditions

Ethanol is an attractive oxygenate increasingly used for blending with petroleum-derived gasoline yielding beneficial combustion and emissions behavior for a range of internal combustion engine schemes, including stoichiometric spark-ignition and low temperature combustion (LTC). As such, it is important to fundamentally understand the autoignition behavior of gasoline/ethanol blends. This work utilizes a rapid compression machine (RCM) and a homogeneous charge compression ignition (HCCI) engine to experimentally quantify changes in fuel reactivity, through ignition delay times and preliminary heat release, for blends of 0 to 30% vol./vol. into a full boiling range research gasoline (FACE-F). Diluted/stoichiometric and undiluted/fuel-lean conditions are explored covering a wide range of compressed temperatures and pressures relevant to conventional and advanced, gasoline combustion engines. Detailed chemical kinetic modeling is undertaken using a recently updated gasoline surrogate model in conjunction with a five-component surrogate to model the RCM experiments and provide chemical insight into the perturbative effects of ethanol on the autoignition process. The diluted/stoichiometric RCM measurements reveal that within the low-temperature regime ethanol retards first-stage and main ignition delay times, and suppresses both the rates and extents of low-temperature heat release (LTHR), while within the intermediate-temperature regime ethanol only causes slight changes. Good agreement of ignition delay time and preliminary heat release prediction is found between model and experimental results. Sensitivity and flux analyses further show that ethanol blending effects are dominated by the competition between the H-atom abstraction from ethanol and other fuel components by OH radical at low temperatures and by HO 2 radical at intermediate temperatures. These findings are consistent across both fuel loading conditions explored in this study. In addition, when HCCI engine experiments are mapped onto undiluted/lean RCM measurements under a constant combustion phasing scenario, good correspondence between the two apparatuses is observed for LTHR and start of high-temperature heat release. Finally, the current study highlights the importance of characterizing LTHR in predicting fuel behaviors in high-boost/low-temperature engines, and demonstrates that RCM experiments can provide an alternative, and more-efficient avenue for such characterization.

02 PETROLEUM↗
DOE OSTI2014

A real-time laser feedback control method for the three-wave laser source used in the polarimeter-interferometer diagnostic on Joint-TEXT tokamak

A three-wave laser polarimeter-interferometer, equipped with three independent far-infrared laser sources, has been developed on Joint-TEXT (J-TEXT) tokamak. The diagnostic system is capable of high-resolution temporal and phase measurement of the Faraday angle and line-integrated density. However, for long-term operation (>10 min), the free-running lasers can lead to large drifts of the intermediate frequencies (∼100–∼500 kHz/10 min) and decay of laser power (∼10%–∼20%/10 min), which act to degrade diagnostic performance. In addition, these effects lead to increased maintenance cost and limit measurement applicability to long pulse/steady state experiments. To solve this problem, a real-time feedback control method of the laser source is proposed. By accurately controlling the length of each laser cavity, both the intermediate frequencies and laser power can be simultaneously controlled: the intermediate frequencies are controlled according to the pre-set values, while the laser powers are maintained at an optimal level. Based on this approach, a real-time feedback control system has been developed and applied on J-TEXT polarimeter-interferometer. Long-term (theoretically no time limit) feedback of intermediate frequencies (maximum change less than ±12 kHz) and laser powers (maximum relative power change less than ±7%) has been successfully achieved.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory-based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH 2 OO, CH 3 CHOO, (CH 3 ) 2 COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene-derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH 2 OO and (CH 3 ) 2 COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever-growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing 1 ππ* state, and how this varies with CI, with conformer and with excitation wavelength. Furthermore, the later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo-induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non-adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Diagnostic development for parallel wave-number measurement of lower hybrid waves in EAST

An eight-channel magnetic probe diagnostic system has been designed and installed adjacent to the 4.6 GHz lower hybrid (LH) grill antenna in the low-field side of the EAST tokamak in order to study the n|| evolution of lower hybrid waves in the first pass from the launcher to the core plasma. The magnetic probes are separated by 6.6 mm, which allows measurement of the dominant parallel refractive index n|| up to n|| =5 for 4.6GHz LH waves. The magnetic probes are designed to be sensitive to the magnetic field component perpendicular to the background magnetic field with a slit on the casing that encloses the probe. The intermediate frequency (IF) stage, which consists of two mixing stages, down-coverts the frequency of the measured wave signals at 4.6 GHz to 20 MHz. A bench test demonstrates the phase stability of the magnetic probe diagnostic system. By evaluating the phase variation of the measured signals along the background magnetic field, the dominant n|| of the LH wave in the scrape-off layer (SOL) has been deduced during the 2019 experimental campaign. In the low density plasma, the measured dominant n|| of the lower hybrid waves is about 2.1, corresponding to the main peak 2.04 of the launched n|| spectrum. The n|| deduced by the least square linear fit method remains near this value in the low density plasma with a high spatial correlation magnitude of 0.9. With an eight-channel probe system a wave-number spectrum has also been deduced, which has a peak near to the measured dominant n||.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1989

Computer simulation of dust grain evolution

The latest results are reported from a Monte Carlo code that is being developed at NASA Ames. The goal of this program, is to derive from the observed and presumed properties of the interstellar medium (ISM) the following information: (1) the size spectrum of interstellar dust; (2) the chemical structure of interstellar dust; (3) interstellar abundances; and (4) the lifetime of a dust grain in the ISM. Presently this study is restricted to refractory interstellar material, i.e., the formation and destruction of ices are not included in the program. The program is embedded in an analytic solution for the bulk chemical evolution of a two-phase interstellar medium in which stars are born in molecular clouds, but new nucleosynthesis products and stellar return are entered into a complementary intercloud medium. The well-mixed matter of each interstellar phase is repeatedly cycled stochastically through the complementary phase and back. Refractory dust is created by thermal condensation as stellar matter flows away from sites of nucleosynthesis such as novae and supernovae and/or from the matter returned from evolved intermediate stars. The history of each particle is traced by standard Monte Carlo techniques as it is sputtered and fragmented by supernova shock waves in the intercloud medium. It also accretes an amorphous mantle of gaseous refractory atoms when its local medium joins with the molecular cloud medium. Finally it encounters the possibility of astration (destruction by star formation) within the molecular clouds.

Liffman, K.↗
NASA NTRS2017

Shergottite Lead Isotope Signature in Chassigny and the Nakhlites

The nakhlites/chassignites and the shergottites represent two differing suites of basaltic martian meteorites. The shergottites have ages less than or equal to 0.6 Ga and a large range of initial Sr-/Sr-86 and epsilon (Nd-143) ratios. Conversely, the nakhlites and chassignites cluster at 1.3-1.4 Ga and have a limited range of initial Sr-87/Sr-86 and epsilon (Nd-143). More importantly, the shergottites have epsilon (W-182) less than 1, whereas the nakhlites and chassignites have epsilon (W-182) approximately 3. This latter observation precludes the extraction of both meteorite groups from a single source region. However, recent Pb isotopic analyses indicate that there may have been interaction between shergottite and nakhlite/chassignite Pb reservoirs.Pb Analyses of Chassigny: Two different studies haveinvestigated 207Pb/204Pb vs. 206Pb/204Pb in Chassigny: (i)TIMS bulk-rock analyses of successive leaches and theirresidue [3]; and (ii) SIMS analysis of individual minerals[4]. The bulk-rock analyses fall along a regression of SIMSplagioclase analyses that define an errorchron that is olderthan the Solar System (4.61±0.1 Ga); i.e., these define amixing line between Chassigny’s principal Pb isotopic components(Fig. 1). Augites and olivines in Chassingy (notshown) also fall along or near the plagioclase regression [4].This agreement indicates that the whole-rock leachateslikely measure indigenous, martian Pb, not terrestrial contamination[5]. SIMS analyses of K-spars and sulfides definea separate, sub-parallel trend having higher 207Pb/206Pbvalues ([4]; Fig. 1). The good agreement between the bulkrockanalyses and the SIMS analyses of plagioclases alsoindicates that the Pb in the K-spars and sulfides cannot be amajor component of Chassigny.The depleted reservoir sampled by Chassigny plagioclaseis not the same as the solar system initial (PAT) andrequires a multi-stage origin. Here we show a two-stagemodel (Fig. 1) with a 238U/204Pb (μ) of 0.5 for 4.5-2.4 Gaand a μ of 7 for 2.4-1.4 Ga. This is not a unique model butdoes produce a Pb composition that falls on the plagioclaseregression at 1.4 Ga, the approximate igneous age of Chassigny [1]. It should be noted that low-μ single-stage modelsare not capable of producing sufficiently radiogenic 206Pb/204Pb at 1.4 Ga.Relation to Shergottites: The Chassigny K-spars and sulfides fall along a second mixing line defined by leachesand residues of depleted and intermediate shergottites [6]. This mixing line falls above the plagioclase regression.Therefore, we also interpret the radiogenic component of this mixing line to represent indigenous martian Pb. It ispossible that the depleted and intermediate shergottites and the Chassigny plagioclases sample radiogenic Pb from thethe same source, i.e., the mixing lines may intersect at high 206Pb/204Pb.Both K-spar and sulfide are late-stage phases. At the time of their crystallization, the Chassigny system appearsto have remained open to a depleted shergottite Pb reservoir. The depleted component of the shergottite mixing linecan be generated by a single-stage evolution from PAT (4.5 to 1.4 Ga) in a reservoir having a μ ~2. A similar modelfor the most depleted shergottites is also possible: μ = 1.5 for 4.5 to 0.3 Ga.Nakhlites: Nakhlite analyses plot between the shergottite and Chassigny plagioclase regressions [3]. So again,members of the nakhlite/chassignite suite show affinities to shergottite Pb.

Jones, J. H.↗
NASA NTRS2014

Design and Implementation of a Deep Space Communications Complex Downlink Array

This paper describes the design and implementation of a frequency domain beamformer that will downlink array the signals of up to eight 34-m or 70-m antennas at each of NASA’s three Deep Space Communications Complexes (DSCC). The array digitizes inputs with an Intermediate Frequency (IF) of 100 to 600 MHz, coherently combines the inputs digitally, and transforms the combined waveform back to analog. Real-time correlation measurements are used for delay and phase calibration, allowing the system to adjust for atmospheric variations. A DSCC Downlink Array system is operational at each DSCC. Initial results from passes with the New Horizons spacecraft are presented and system performance is analyzed.

Wang, Douglas↗