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At least 1,171 records · Page 65

Development of a Linear Ion Trap Mass Spectrometer (LITMS) Investigation for Future Planetary Surface Missions

Future surface missions to Mars and other planetary bodies will benefit from continued advances in miniature sensor and sample handling technologies that enable high-performance chemical analyses of natural samples. Fine-scale (approx.1 mm and below) analyses of rock surfaces and interiors, such as exposed on a drill core, will permit (1) the detection of habitability markers including complex organics in association with their original depositional environment, and (2) the characterization of successive layers and gradients that can reveal the time-evolution of those environments. In particular, if broad-based and highly-sensitive mass spectrometry techniques could be brought to such scales, the resulting planetary science capability would be truly powerful. The Linear Ion Trap Mass Spectrometer (LITMS) investigation is designed to conduct fine-scale organic and inorganic analyses of short (approx.5-10 cm) rock cores such as could be acquired by a planetary lander or rover arm-based drill. LITMS combines both pyrolysis/gas chromatograph mass spectrometry (GCMS) of sub-sampled core fines, and laser desorption mass spectrometry (LDMS) of the intact core surface, using a common mass analyzer, enhanced from the design used in the Mars Organic Molecule Analyzer (MOMA) instrument on the 2018 ExoMars rover. LITMS additionally features developments based on the Sample Analysis at Mars (SAM) investigation on MSL and recent NASA-funded prototype efforts in laser mass spectrometry, pyrolysis, and precision subsampling. LITMS brings these combined capabilities to achieve its four measurement objectives: (1) Organics: Broad Survey Detect organic molecules over a wide range of molecular weight, volatility, electronegativity, concentration, and host mineralogy. (2) Organic: Molecular Structure Characterize internal molecular structure to identify individual compounds, and reveal functionalization and processing. (3) Inorganic Host Environment Assess the local chemical/mineralogical makeup of organic host phases to help determine deposition and preservation factors. (4) Chemical Stratigraphy Analyze the fine spatial distribution and variation of key species with depth.

Mars↗

Surface spins enhanced magnetoelectric coefficient and impedance spectroscopy of BaFe{sub 0.01}Ti{sub 0.99}O{sub 3} and BaFe{sub 0.015}Ti{sub 0.985}O{sub 3} nanorods

Highlights: • Multiferroic Fe-doped BaTiO{sub 3} nanorods. • Sol–gel. • Magnetoelectric coefficient. • Transmission electron microscopy. • Cole–Cole plots. - Abstract: Multiferroic BaFe{sub 0.01}Ti{sub 0.99}O{sub 3} (BFT1) and BaFe{sub 0.015}Ti{sub 0.985}O{sub 3} (BFT15) nanorods were prepared by a sol–gel synthesis and annealed at 700 °C/2 h. The tetragonal phase and nano dimensions of BFT samples are identified by X-ray diffraction and transmission electron microscopy. The enhancement in ferroelectricity depends upon low porosity, tetragonal phase, space charge field, larger surface area and oriented growth. The ferromagnetism depends upon partially filled inner shells, surface spins and oxygen vacancies. The magnetoelectric coefficient is explained on the basis of surface spins, short-range interactions near surface boundary, compressive stress and twin structure contributed by nano grains which can reside stress near grain boundaries. The frequency dependent real (Z′) and imaginary (Z″) parts of impedance spectra are confirmed by the variations that observed in dielectric properties. The values of resistance of grain boundaries, R{sub gb} is higher than grains, R{sub g} indicating that the effect of grain boundaries is dominant in BFT nanorods.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High-Throughput Characterization and Optimization of Polyamide Hydrolase Activity Using Open Port Sampling Interface Mass Spectrometry

Enzymatic biodegradation of polymers, such as polyamides (PA), has the potential to cost-effectively reduce plastic waste, but enhancements in degradation efficiency are needed. Engineering enzymes through directed evolution is one pathway toward identification of critical domains needed for improving activity. However, screening such enzymatic libraries (100s-to-1000s of samples) is time-consuming. Here we demonstrate the use of robotic autosampler (PAL) and immediate drop on demand technology (I.DOT) liquid handling systems coupled with open-port sampling interface-mass spectrometry (OPSI-MS) to screen for PA6 and PA66 hydrolysis by 6-aminohexanoate-oligomer endo-hydrolase (nylon hydrolase, NylC) in a high-throughput (8–20 s/sample) manner. The OPSI-MS technique required minimal sample preparation and was amenable to 96-well plate formats for automated processing. Enzymatic hydrolysis of PA characteristically produced soluble linear oligomer products that could be identified by OPSI-MS. Incubation temperatures and times were optimized for PA6 (65 °C, 24 h) and PA66 (75 °C, 24 h) over 108 experiments. In addition, the I.DOT/OPSI-MS quantified production of PA6 linear dimer (8.3 ± 1.6 μg/mL) and PA66 linear monomer (13.5 ± 1.5 μg/mL) by NylC with a lower limit of detection of 0.029 and 0.032 μg/mL, respectively. For PA6 and PA66, linear oligomer production corresponded to 0.096 ± 0.018% and 0.204 ± 0.028% conversion of dry pellet mass, respectively. The developed methodology is expected to be utilized to assess enzymatic hydrolysis of engineered enzyme libraries, comprising hundreds to thousands of individual samples.

47 OTHER INSTRUMENTATION↗

Resource Prospector Instrumentation for Lunar Volatiles Prospecting, Sample Acquisition and Processing

Data gathered from lunar missions within the last two decades have significantly enhanced our understanding of the volatile resources available on the lunar surface, specifically focusing on the polar regions. Several orbiting missions such as Clementine and Lunar Prospector have suggested the presence of volatile ices and enhanced hydrogen concentrations in the permanently shadowed regions of the moon. The Lunar Crater Observation and Sensing Satellite (LCROSS) mission was the first to provide direct measurement of water ice in a permanently shadowed region. These missions with other orbiting assets have laid the groundwork for the next step in the exploration of the lunar surface; providing ground truth data of the volatiles by mapping the distribution and processing lunar regolith for resource extraction. This next step is the robotic mission Resource Prospector (RP). Resource Prospector is a lunar mission to investigate 'strategic knowledge gaps' (SKGs) for in-situ resource utilization (ISRU). The mission is proposed to land in the lunar south pole near a permanently shadowed crater. The landing site will be determined by the science team with input from broader international community as being near traversable landscape that has a high potential of containing elevated concentrations of volatiles such as water while maximizing mission duration. A rover will host the Regolith & Environment Science and Oxygen & Lunar Volatile Extraction (RESOLVE) payload for resource mapping and processing. The science instruments on the payload include a 1-meter drill, neutron spectrometer, a near infrared spectrometer, an operations camera, and a reactor with a gas chromatograph-mass spectrometer for volatile analysis. After the RP lander safely delivers the rover to the lunar surface, the science team will guide the rover team on the first traverse plan. The neutron spectrometer (NS) and near infrared (NIR) spectrometer instruments will be used as prospecting tools to guide the traverse path. The NS will map the water-equivalent hydrogen concentration as low as 0.5% by weight to an 80 centimeter depth as the rover traverses the lunar landscape. The NIR spectrometer will measure surficial H2O/OH as well as general mineralogy. When the prospecting instruments identify a potential volatile-rich area during the course of a traverse, the prospect is then mapped out and the most promising location identified. An augering drill capable of sampling to a depth of 100 centimeters will excavate regolith for analysis. A quick assay of the drill cuttings will be made using an operations camera and NIR spectrometer. With the water depth confirmed by this first auguring activity, a regolith sample may be extracted for processing. The drill will deliver the regolith sample to a crucible that will be sealed and heated. Evolved volatiles will be measured by a gas chromatograph-mass spectrometer and the water will be captured and photographed. RP is a solar powered mission, which given the polar location translates to a relatively short mission duration on the order of 4-15 days. This short mission duration drives the concept of operations, instrumentation, and data analysis towards critical real time analysis and decision support. Previous payload field tests have increased the fidelity of the hardware, software, and mission operations. Current activities include a mission level field test to optimize interfaces between the payload and rover as well as better understand the interaction of the science and rover teams during the mission timeline. This paper will include the current status of the science instruments on the payload as well as the integrated field test occurring in fall of 2015. The concept of operations will be discussed, including the real time science and engineering decision-making process based on the critical data from the instrumentation. The path to flight will be discussed with the approach to this ambitious low cost mission.

ISRU↗

Hot deformation induced defects and performance enhancement in FeSb{sub 2} thermoelectric materials

The effect of hot deformation induced defects and texture on thermoelectric properties of FeSb{sub 2} bulk crystals has been investigated. The transport properties of the samples along both parallel and perpendicular direction of pressing were measured from 3 K to 300 K. The results showed that thermal conductivity of the deformed samples was significantly reduced. After twice deformation, the thermal conductivity of the sample along the perpendicular direction of pressing was decreased to 4 W/mK, which was only one third of that before deformation. Transmission electron microscopy observation revealed the presence of high density of lattice defects in the deformed samples. The lattice thermal conductivity was analyzed using the Debye-Callaway approximation, and the results showed that the deformation induced lattice imperfections play an important role in enhancing phonon scattering. In addition, both the electrical resistivity and Seebeck coefficient exhibited a weak anisotropy in the deformed samples. The figure of merit ZT of the bulk FeSb{sub 2} was significantly improved from 0.010 to 0.021 after deformation.

36 MATERIALS SCIENCE↗

Core-shell structured α-Fe2O3@CeO2 heterojunction for the enhanced visible-light photocatalytic activity

Highlights: • CeO{sub 2}–coated α-Fe{sub 2}O{sub 3} sample was prepared via a hydrothermal route. • α-Fe{sub 2}O{sub 3}@CeO{sub 2} presented the excellent photocatalytic activity and stability. • The heterojunction interface facilitated the separation of electron-hole pairs. • Ce{sup 4+}/Ce{sup 3+} redox couple promoted the efficient electron transfer. - Abstract: CeO{sub 2}-coated α-Fe{sub 2}O{sub 3} nanoparticles (α-Fe{sub 2}O{sub 3}@CeO{sub 2}) with the enhanced photocatalytic activity were synthesized by a hydrothermal route and performed for the visible light driven photo-degradation of methylene blue (MB). The photocatalytic activity of α-Fe{sub 2}O{sub 3}@CeO{sub 2} is greatly affected by the thickness of CeO{sub 2} shell under the same conditions. The core-shell structured α-Fe{sub 2}O{sub 3}@CeO{sub 2} sample exhibited a narrower band gap energy in comparison to the pure α-Fe{sub 2}O{sub 3} and CeO{sub 2} bulks, leading to the excellent photocatalytic activity and stability for the degradation of MB under visible light irradiation after five cycle times. The core-shell structured α-Fe{sub 2}O{sub 3}@CeO{sub 2} sample presented higher degradation activity than that of the supported 8-Fe/CeO{sub 2} bulks with optimized α-Fe{sub 2}O{sub 3} loading of 8%. It can be ascribed to the Ce{sup 4+}/Ce{sup 3+} redox couple and the heterojunction interfaces of core-shell structured α-Fe{sub 2}O{sub 3}@CeO{sub 2} sample, which can promote the electrons transfer and restrain the photoexcited electron-hole recombination, leading to the excellent degradation activity under visible light irradiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Solidification pattern, microstructure and texture development in Laser Powder Bed Fusion (LPBF) of Al10SiMg alloy

Highlights: • The complex solidification pattern during Laser Powder Bed Fusion of Al10SiMg alloy is explained. • The evolution of α-Al cellular network, grain structure and texture development is characterized. • The grain structure is shown to be columnar throughout the printed sample • The grains’ orientation align with that of the α-Al cells. • The size evolution of α-Al cells and grains within the scan tracks follow opposite patterns. • Utilizing of a 67° hatch angle enhances densification and promotes a more isotropically developed texture across the build. - Abstract: A comprehensive analysis of solidification patterns and microstructural development is presented for an Al10SiMg sample produced by Laser Powder Bed Fusion (LPBF). Utilizing a novel scanning strategy that involves counter-clockwise rotation of the scan vector by 67° upon completion of each layer, a relatively randomized cusp-like pattern of protruding/overlapping scan tracks has been produced along the build direction. We show that such a distribution of scan tracks, as well as enhancing densification during LPBF, reduces the overall crystallographic texture in the sample, as opposed to those normally achieved by commonly-used bidirectional or island-based scanning regimes with 90° rotation. It is shown that, under directional solidification conditions present in LPBF, the grain structure is strictly columnar throughout the sample and that the grains' orientation aligns well with that of the α-Al cells. The size evolution of cells and grains within the melt pools, however, is shown to follow opposite patterns. The cells'/grains' size distribution and texture in the sample are explained via use of analytical models of cellular solidification as well as the overall heat flow direction and local solidification conditions in relation to the LPBF processing conditions. Such a knowledge of the mechanisms upon which microstructural features evolve throughout a complex solidification process is critical for process optimization and control of mechanical properties in LPBF.

36 MATERIALS SCIENCE↗

The effect of secondary phases on microstructure and irradiation damage in an as-built additively manufactured 316 L stainless steel with a hafnium compositional gradient

Additive manufacturing (AM) or rapid prototyping has become a crucial tool for reducing both cost and time while increasing efficiency in qualifying structural materials for reactor use. In this study, directed energy deposition (DED) was used to develop an as-built 316 L stainless steel sample with three regions of increasing Hf-dopant to study the effects of Hf on the irradiation response of the material. Morphological and microstructural changes were analyzed before and after 2 MeV proton irradiation at 360 °C to a damage of 2.5 dpa at ~ 10 µm below the surface. The addition of Hf effectively suppressed radiation-induced damage (dislocation loops, radiation-induced segregation) due to enhanced point defect recombination. The radiation damage seen in the as-built sample was further compared to a thermo-mechanically treated counterpart of the same fabrication and irradiation parameters which was found to behave superiorly. In conclusion, the increased radiation resistance of this material may be attributed to the as-built microstructure, which includes undissolved Hf particles, delta ferrite grains and cellular sub-grain boundaries that can hinder defect motion.

316L Stainless Steel↗

Study of Photocatalytic Nano-Particle Effects on the Low Temperature Plasma Ionization Mass Spectrometry

Although the low temperature plasma mass spectrometry (LTP-MS) is widely used as an analysis tool for many biochemical samples, its application window is somehow limited to the analytes of low molecular mass and high volatility. For this reason, there have been attempts to enhance the ionization/desorption efficiencies with extra heating, for instance. In this study, another enhancement method was suggested using the photocatalytic nano-particles (NPs). In order to assess the NP effects on the LTP-MS, two fatty acid ethyl ester samples of ethyl myristate and ethyl palmitate were used, and the NP of titanium dioxide (TiO{sub 2}) was mainly employed. The results showed that the signal intensities of the LTP-MS were largely increased with the TiO{sub 2} addition for both samples. In addition, the cholesterol sample was analyzed using the TiO{sub 2} assisted LTP-MS, also resulting in the enhancement of the signal intensity. The overall results inferred that the photocatalytic NP confirmed its role as an effective assist tool for the LTP-MS, especially suitable because of the facile method and the heat-free nature. .

77 NANOSCIENCE AND NANOTECHNOLOGY↗

13C NMR spectroscopy of the insoluble carbon of carbonaceous chondrites

13C NMR spectra have been obtained of the insoluble carbon residues resulting from HF-digestion of three carbonaceous chondrites, Orgueil (C1), Murchison (CM2), and Allende (CV3). Spectra obtained using the cross polarization magic-angle spinning technique show two major features attributable respectively to carbon in aliphatic/olefinic structures. The spectrum obtained from the Allende sample was weak, presumably as a consequence of its low hydrogen content. Single pulse excitation spectra, which do not depend on 1H-13C polarization transfer for signal enhancement were also obtained. These spectra, which may be more representative of the total carbon in the meteorite samples, indicate a greater content of carbon in aromatic/olefinic structures. These results suggest that extensive polycyclic aromatic sheets are important structural features of the insoluble carbon of all three meteorites. The Orgueil and Murchison materials contain additional hydrogenated aromatic/olefinic and aliphatic groups.

Non-NASA Center↗

Ubiquitous short-range order in multi-principal element alloys

Recent research in multi-principal element alloys (MPEAs) has increasingly focused on the role of short-range order (SRO) on material performance. However, the mechanisms of SRO formation and its precise control remain elusive, limiting the progress of SRO engineering. Here, leveraging advanced additive manufacturing techniques that produce samples with a wide range of cooling rates (up to 10 7 K s –1 ) and an enhanced semi-quantitative electron microscopy method, we characterize SRO in three CoCrNi-based face-centered-cubic (FCC) MPEAs. Surprisingly, irrespective of the processing and thermal treatment history, all samples exhibit similar levels of SRO. Atomistic simulations reveal that during solidification, prevalent local chemical order arises in the liquid-solid interface (solidification front) even under the extreme cooling rate of 10 11 K s –1 . This phenomenon stems from the swift atomic diffusion in the supercooled liquid, which matches or even surpasses the rate of solidification. Therefore, SRO is an inherent characteristic of most FCC MPEAs, insensitive to variations in cooling rates and even annealing treatments typically available in experiments.

36 MATERIALS SCIENCE↗

Heterogeneous in-situ nanostructure contributes to the thermoelectric performance of Zn{sub 4}Sb{sub 3}

Single-phase Zn{sub 4}Sb{sub 3} and ZnSb-containing samples were prepared by Plasma Activated Sintering. An abrupt decrease of thermal conductivity was found at about 400 K, which is attributed to the microstructure change of Zn{sub 4}Sb{sub 3}. Nanoscale inclusions and compositional inhomogeneities were found in Zn{sub 4}Sb{sub 3} sample at 473 K by high-resolution transmission electron microscopy. The phonon scattering is enhanced by increasing grain boundaries and chaotic structure, which reduces the thermal conductivity and increases the thermoelectric performance of Zn{sub 4}Sb{sub 3} at elevated temperature. The Rietveld refinement results show that large ZnSb grains in ZnSb-containing samples will accommodate excess Zn atoms, and then reduce thermoelectric performance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interacting galaxies resolved by IRAS

We discuss procedures, limitations and results of high resolution processing of interacting galaxies observed by the Infrared Astronomical Satellite (IRAS). Among 56 potentially resolvable interacting groups selected from the IRAS Bright Galaxy Sample, 22 systems have been resolved yielding fluxes for a total of 51 galaxies. In about 2/3 of the resolved pairs, both galaxies were detected in the far-infrared. A set of isolated non-interacting galaxies was chosen from the Bright Galaxy Sample for comparison with the interacting galaxies. For the current sample, which naturally excludes close pairs and ultraluminous merging systems, the primary conclusions are: (1) It is not possible to distinguish individual interacting galaxies from isolated galaxies of similar luminosity on the basis of infrared properties alone. (2) No direct correlation was found between measures of interaction strength and indicators of enhanced star formation within the resolved systems. (3) Comparison of the interacting and isolated samples indicates statistically significant differences between their distributions of far-infrared color ratios, luminosities, and surface brightnesses. Even during the early stages of interaction spanned by these systems, in a statistical sense, tidal perturbations substantially boost far-infrared indicators of star formation compared to non-interacting systems. We also briefly discuss future prospects for pushing the IRAS data to its limits for additional interacting systems.

Mazzarella, Joseph M.↗

Volcanic rocks and the geologic history of Mars

A number of questions exist regarding the geology of Mars which can be addressed by the proposed Mars rover-sample return mission. The use of a rover during the proposed mission greatly enhances the ability to investigate multiple aspects of Martian geology and geological history. Attempting to address all of the important questions may dilute the amount of information that can be obtained regarding each question and may result in no satisfactory answers. Prioritization is essential to a successful mission. The task of setting priorities is simplified somewhat when it is considered that answers to some of these questions do not require taking samples, and that for some questions, sample location is not as important as for others. The surface of Mars presents two distinct terrains, both of which have the potential to contain valuable information regarding the composition of Mars.

Salpas, P. A.↗

The Role of Zn in Chalcopyrite CuFeS 2 : Enhanced Thermoelectric Properties of Cu 1– x Zn x FeS 2 with In Situ Nanoprecipitates

Chalcopyrite (CuFeS 2 ) is a widespread natural mineral, composed of earth–abundant and nontoxic elements. It has been considered a promising n–type material for thermoelectric applications. In this work, a series of Zn–doped Cu 1–x Zn x FeS 2 (x = 0–0.1) compounds are synthesized by vacuum melting combined with the plasma activated sintering process. The role of Zn in the chalcopyrite and its different effects on thermoelectric properties, depending on its concentration and location in the crystal lattice, are discussed. It is found that Zn is an effective donor which increases the carrier concentration and improves the thermoelectric properties of CuFeS 2 . Here, when the content of Zn exceeds the solubility limit, Zn partially enters the Cu sites and forms in situ ZnS nanophase. This, in turn, shifts the balance between the anion and cation species which is re–established by the formation of antisite Fe/Cu defects. Beyond maintaining charge neutrality of the structure, such antisite defects relieve the lattice strain in the matrix and increase the solubility of Zn further. The highest ZT value of 0.26 is achieved at 630 K for Cu 0.92 Zn 0.08 FeS 2 , which represents an enhancement of about 80% over that of the pristine CuFeS 2 sample.

36 MATERIALS SCIENCE↗

Surface Treatment of Powder-Bed Fusion Additive Manufactured Metals for Improved Fatigue Life

High-cycle fatigue (HCF) tests were conducted on samples fabricated by two powder-bed additive manufacturing techniques. Samples were tested with as-produced surfaces and after various non-contact surface improvement treatments. Ti-6Al-4V samples were made using both electron beam melting (EBM) and selective laser melting (SLM), while Inconel 625 was fabricated using SLM. Ti-6Al-4V was treated with a commercial chemically accelerated vibratory polishing process, with target material removal of approximately 200 µm from each surface for EBM samples and 100 µm for SLM samples. This technique led to increases in both the number of cycles before failure at a given loading condition and endurance limit (at 10{sup 7} cycles) compared to samples with as-produced surfaces. The results are interpreted as the reduction in elastic stress concentration factor associated with surface defects where fatigue cracks initiate. SLM 625 was treated with both an abrasive polishing method and laser surface remelting. Both methods led to improvements in surface roughness, but these did not lead to improvements in fatigue properties of SLM 625. For abrasive polished samples, the combination of improved measured surface roughness without fatigue property enhancement suggests that surface material is removed, but the roots of surface defects, where fatigue cracks initiate, were left intact. For laser treatment, the remelted surface layer retained a rapidly solidified microstructure that did not increase the number of cycles before crack initiation even though the surface was smoother compared to the surface prior to polishing.

36 MATERIALS SCIENCE↗

Cost-effective fabrication of ZnO/g-C3N4 composite film coated stainless steel meshes for visible light responsive photocatalysis

Highlights: • First report on the photocatalytic efficacy of ZnO/g-C{sub 3}N{sub 4} composite thin film coated stainless steel mesh. • A homemade automated tubular nebulizer spray pyrolysis technique is used to deposit the samples. • All supplementary studies (SEM, XPS, FTIR and PL) support the enhancement photocatalytic activity. - Abstract: The ZnO and ZnO/g-C{sub 3}N{sub 4} composite films were deposited on stainless steel meshes having different apertures (370, 500, 780 and 1000 μm) using a simple cost-effective automated tubular nebulizer spray pyrolysis technique for photocatalytic degradation of organic pollutants. Photocatalytic studies were done for the degradation of methylene blue (MB) and malachite green (MG). The photocatalytic studies reveal that the ZnO/g-C{sub 3}N{sub 4} composite film having smallest aperture exhibits superior photocatalytic activity compared with other meshes. The degradation efficiency of this composite film for MB and MG dyes are 97% (irradiation time-75 min) and 95% (irradiation time-45 min), whereas for pristine ZnO film the corresponding efficiencies are only 88% and 87%. The aperture size related photocatalytic efficiency variations and the effect of g-C{sub 3}N{sub 4} addition on the photocatalytic efficiency of ZnO films have been addressed with appropriate supporting experimental evidences and reports.

36 MATERIALS SCIENCE↗