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At least 505 records · Page 28

Low Thermal Conductivity in Heteroanionic Materials with Layers of Homoleptic Polyhedra

Although BiAgOSe, an analogue of a well-studied thermoelectric material BiCuOSe, is thermodynamically stable, its synthesis is complicated by the low driving force of formation from the stable binary and ternary intermediates. Here we have developed a “subtraction strategy” to suppress byproducts and produce pure phase BiAgOSe using hydrothermal methods. Electronic structure calculations and optical characterization show that BiAgOSe is an indirect bandgap semiconductor with a bandgap of 0.95 eV. The prepared sample exhibits lower lattice thermal conductivities (0.61 W·m –1 ·K –1 at room temperature and 0.35 W·m –1 ·K –1 at 650 K) than BiCuOSe. Further, lattice dynamical simulations and variable temperature diffraction measurements demonstrate that the low lattice thermal conductivity arises from both the low sound velocity and high phonon–phonon scattering rates in BiAgOSe. These in turn result primarily from the soft Ag–Se bonds in the edge-sharing AgSe 4 tetrahedra and large sublattice mismatch between the quasi-two-dimensional [Bi 2 O 2 ] 2+ and [Ag 2 Se 2 ] 2– layers. These results highlight the advantages of manipulating the chemistry of homoleptic polyhedra in heteroanionic compounds for electronic structure and phonon transport control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monitoring and control technologies for bioregenerative life support systems/CELSS

The development of a controlled Ecological Life Support System (CELSS) will require NASA to develop innovative monitoring and control technologies to operate the different components of the system. Primary effort over the past three to four years has been directed toward the development of technologies to operate a biomass production module. Computer hardware and software required to operate, collect, and summarize environmental data for a large plant growth chamber facility were developed and refined. Sensors and controls required to collect information on such physical parameters as relative humidity, temperature, irradiance, pressure, and gases in the atmosphere; and PH, dissolved oxygen, fluid flow rates, and electrical conductivity in the nutrient solutions are being developed and tested. Technologies required to produce high artificial irradiance for plant growth and those required to collect and transport natural light into a plant growth chamber are also being evaluated. Significant effort was directed towards the development and testing of a membrane nutrient delivery system required to manipulate, seed, and harvest crops, and to determine plant health prior to stress impacting plant productivity are also being researched. Tissue culture technologies are being developed for use in management and propagation of crop plants. Though previous efforts have focussed on development of technologies required to operate a biomass production module for a CELSS, current efforts are expanding to include technologies required to operate modules such as food preparation, biomass processing, and resource (waste) recovery which are integral parts of the CELSS.

Knott, William M.↗

Developing a Hybrid Space Suit Simulator as a Research Tool for Assessing Extravehicular Activity Relevant Workload

Suited testing time is limited and hard to come by, expensive, and requires a whole team to operate and monitor the suit; however, pressurized spacesuits are not always necessary for initial developmental efforts or assessment of informatics. The Human Physiology, Performance, Protection & Operations Laboratory (H-3PO) at NASA Johnson Space Center (JSC) is developing a Hybrid Space Suit Simulator (HS3) to support characterization of human performance during planetary surface exploration analogs. The primary goal of HS3 is to create a low cost, modular, and unpressurized suit simulator for use as a research tool which provides relevant physical and cognitive workload approximations with EVA-like immersion during planetary extravehicular activity (EVA) simulations. HS3 consists of a soft suit, communication, thermal control, gloves, boots, helmet, and integrated bioinformatics/sensors. The modular design of HS3 allows it to be modified to support test objectives as needed. HS3 enables H-3PO and NASA to complete critical human health and performance testing to address open risks and knowledge gaps in a timely, repeatable, and controlled manner. Four engineering runs were completed with HS3 as a baseline for capability. General workload was assessed while traversing on a passive treadmill and conducting geology tasks. Liquid cooling temperature, suit temperature, and metabolic rates were collected during one extended three-hour engineering run. For the duration of the engineering run the suit temperature was 26.6 ± 1.58 °C while suit humidity was 53.7 ± 5.11 %. Helmet temperature was higher than suit temperature at 27.8 ± 1.58 °C. Helmet humidity was lower than average suit humidity at 50.12 ± 11.3 °C. The liquid cooling temperature remained stable at 22.4 ± 1.62 °C. Resting metabolic rate was 597 ± 88 BTU/hr while metabolic rate increased during traverse tasks at 1500 ± 319 BTU/hr and geology tasks at 921 ± 129 BTU/hr. Following the engineering runs, a characterization study will be conducted. The subjects will perform EVA-like scenarios in both a shirtsleeve only and donned HS3, consisting of EVA task circuit focused on traversing, geological rock sampling, and task board manipulation. The characterization study will provide data capability for implementing HS3 in analog EVA testing environments.

Monica Hew↗

Achieving the 1D Atomic Chain Limit in Van der Waals Crystals

Experiments with graphene have demonstrated that 2D van der Waals materials can be stable, robust, and efficiently manipulated at the level of individual atomic planes. However, the stability and manipulation of 1D van der Waals materials and individual atomic chains remains elusive. Here, in this work, the ability to exfoliate and process two representative van der Waals materials containing 1D motifs, namely MoI 3 and Ta 2 Se 8 I, at the scale of individual atomic chains is demonstrated. High‐resolution transmission electron microscopy and atomic force microscopy studies confirm the presence of stable individual atomic chains of MoI 3 at room temperature. It is further shown that 1D van der Waals materials with low exfoliation energy, such as Ta 2 Se 8 I, can be processed with electron beams to achieve suspended individual atomic chains. Ab initio calculations corroborate the findings regarding the cleavage energies and the thermodynamic stability of individual atomic chains in these 1D van der Waals materials. These results demonstrate that the top‐down approach in material processing can be extended to the scale of individual chains.

1D materials↗

Direct Fabrication of Atomically Defined Pores in MXenes Using Feedback-Driven STEM

Controlled fabrication of nanopores in 2D materials offer the means to create robust membranes needed for ion transport and nanofiltration. Techniques for creating nanopores have relied upon either plasma etching or direct irradiation; however, aberration-corrected scanning transmission electron microscopy (STEM) offers the advantage of combining a sub-Å sized electron beam for atomic manipulation along with atomic resolution imaging. Here, for this work, a method for automated nanopore fabrication is utilized with real-time atomic visualization to enhance the mechanistic understanding of beam-induced transformations. Additionally, an electron beam simulation technique, Electron-Beam Simulator (E-BeamSim) is developed to observe the atomic movements and interactions resulting from electron beam irradiation. Using the MXene Ti 3 C 2 T x , the influence of temperature on nanopore fabrication is explored by tracking atomic transformations and find that at room temperature the electron beam irradiation induces random displacement and results in titanium pileups at the nanopore edge, which is confirmed by E-BeamSim. At elevated temperatures, after removal of the surface functional groups and with the increased mobility of atoms results in atomic transformations that lead to the selective removal of atoms layer by layer. This work can lead to the development of defect engineering techniques within functionalized MXene layers and other 2D materials.

36 MATERIALS SCIENCE↗

Greenhouse gas flux response in biochar- and compost-amended urban soils under simulated soil hydrologic dynamics

Understanding greenhouse gas emission dynamics in lawn soils is essential for improving climate change mitigation strategies in urban and suburban environments. This project measured fluxes of carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O) fluxes from turfgrass soil columns amended with biochar, compost, biochar-compost blend, control (no amendment) in a controlled greenhouse mesocosm experiment. This project simulated contrasting water saturation regimes consisting of normal irrigation with sprinkler, transient half or full saturation by water table manipulation, and subsequent drying phase under both sod or seeded grass conditions. Compost-amended columns (compost or biochar-compost blend) exhibited higher average CO 2 fluxes (6 µmol m-2 s-1) compared to biochar or control columns (4.5 – 5.0 µmol m-2 s-1) across all saturation levels under sod conditions. Seeded grass conditions generally resulted in less CO 2 emissions. The CO 2 fluxes were positively correlated with air temperature and negatively correlated with soil moisture. Biochar-amended columns retained high soil moisture (~95 %) throughout experiments, demonstrating superior moisture retention compared to compost. CH 4 and N 2 O fluxes exhibited temporal increases (5-8 nmol m-2 s-1) during saturation and drainage phases, indicating their sensitivity to hydrologic conditions. These findings suggest that temperature and amendment types are primary driver of CO 2 emissions, while CH 4 and N 2 O fluxes are more responsive to water saturation dynamics in lawn soils.

54 ENVIRONMENTAL SCIENCES↗

Use of an adaptable cell culture kit for performing lymphocyte and monocyte cell cultures in microgravity

The results of experiments performed in recent years on board facilities such as the Space Shuttle/Spacelab have demonstrated that many cell systems, ranging from simple bacteria to mammalian cells, are sensitive to the microgravity environment, suggesting gravity affects fundamental cellular processes. However, performing well-controlled experiments aboard spacecraft offers unique challenges to the cell biologist. Although systems such as the European 'Biorack' provide generic experiment facilities including an incubator, on-board 1-g reference centrifuge, and contained area for manipulations, the experimenter must still establish a system for performing cell culture experiments that is compatible with the constraints of spaceflight. Two different cell culture kits developed by the French Space Agency, CNES, were recently used to perform a series of experiments during four flights of the 'Biorack' facility aboard the Space Shuttle. The first unit, Generic Cell Activation Kit 1 (GCAK-1), contains six separate culture units per cassette, each consisting of a culture chamber, activator chamber, filtration system (permitting separation of cells from supernatant in-flight), injection port, and supernatant collection chamber. The second unit (GCAK-2) also contains six separate culture units, including a culture, activator, and fixation chambers. Both hardware units permit relatively complex cell culture manipulations without extensive use of spacecraft resources (crew time, volume, mass, power), or the need for excessive safety measures. Possible operations include stimulation of cultures with activators, separation of cells from supernatant, fixation/lysis, manipulation of radiolabelled reagents, and medium exchange. Investigations performed aboard the Space Shuttle in six different experiments used Jurkat, purified T-cells or U937 cells, the results of which are reported separately. We report here the behaviour of Jurkat and U937 cells in the GCAK hardware in ground-based investigations simulating the conditions expected in the flight experiment. Several parameters including cell concentration, time between cell loading and activation, and storage temperature on cell survival were examined to characterise cell response and optimise the experiments to be flown aboard the Space Shuttle. Results indicate that the objectives of the experiments could be met with delays up to 5 days between cell loading into the hardware and initial in flight experiment activation, without the need for medium exchange. Experiment hardware of this kind, which is adaptable to a wide range of cell types and can be easily interfaced to different spacecraft facilities, offers the possibility for a wide range of experimenters successfully and easily to utilise future flight opportunities.

short duration↗

Embossed Teflon AF Laminate Membrane Microfluidic Diaphragm Valves

A microfluidic system has been designed to survive spaceflight and to function autonomously on the Martian surface. It manipulates microscopic quantities of liquid water and performs chemical analyses on these samples to assay for the presence of molecules associated with past or present living processes. This technology lies at the core of the Urey Instrument, which is scheduled for inclusion on the Pasteur Payload of the ESA ExoMars rover mission in 2013. Fabrication processes have been developed to make the microfabricated Teflon-AF microfluidic diaphragm pumps capable of surviving extreme temperature excursions before and after exposure to liquid water. Two glass wafers are etched with features and a continuous Teflon membrane is sandwiched between them (see figure). Single valves are constructed using this geometry. The microfabricated devices are then post processed by heating the assembled device while applying pneumatic pressure to force the Teflon diaphragm against the valve seat while it is softened. After cooling the device, the embossed membrane retains this new shape. This solves previous problems with bubble introduction into the fluid flow where deformations of the membrane at the valve seat occurred during device bonding at elevated temperatures (100-150 C). The use of laminated membranes containing commercial Teflon AF 2400 sheet sandwiched between spun Teflon AF 1600 layers performed best, and were less gas permeable than Teflon AF 1600 membranes on their own. Spinning Teflon AF 1600 solution (6 percent in FLOURINERT(Registered TradeMark) FC40 solvent, 3M Company) at 500 rpm for 1.5 seconds, followed by 1,000 rpm for 3 seconds onto Borofloat glass wafers, results in a 10-micron-thick film of extremely smooth Teflon AF. This spinning process is repeated several times on flat, blank, glass wafers in order to gradually build a thick, smooth membrane. After running this process at least five times, the wafer and Teflon coating are heated under vacuum at 220 C for one hour in order to drive off any residual solvent present in the composite film. After this, a second blank, glass wafer is brought down from above and the stack is held under vacuum at 3 atm mechanical pressure for ten 10 hours.

Willis, Peter↗

Two-dimensional heavy fermions in the van der Waals metal CeSiI

Heavy-fermion metals are prototype systems for observing emergent quantum phases driven by electronic interactions. A long-standing aspiration is the dimensional reduction of these materials to exert control over their quantum phases, which remains a significant challenge because traditional intermetallic heavy-fermion compounds have three-dimensional atomic and electronic structures. Here we report comprehensive thermodynamic and spectroscopic evidence of an antiferromagnetically ordered heavy-fermion ground state in CeSiI, an intermetallic comprising two-dimensional (2D) metallic sheets held together by weak interlayer van der Waals (vdW) interactions. Owing to its vdW nature, CeSiI has a quasi-2D electronic structure, and we can control its physical dimension through exfoliation. The emergence of coherent hybridization of f and conduction electrons at low temperature is supported by the temperature evolution of angle-resolved photoemission and scanning tunnelling spectra near the Fermi level and by heat capacity measurements. Electrical transport measurements on few-layer fakes reveal heavy-fermion behaviour and magnetic order down to the ultra-thin regime. Importantly, our work establishes CeSiI and related materials as a unique platform for studying dimensionally confined heavy fermions in bulk crystals and employing 2D device fabrication techniques and vdW heterostructures to manipulate the interplay between Kondo screening, magnetic order and proximity effects.

36 MATERIALS SCIENCE↗

Insulation Test Cryostat with Lift Mechanism

A multi-purpose, cylindrical thermal insulation test apparatus is used for testing insulation materials and systems of materials using a liquid boil-off calorimeter system for absolute measurement of the effective thermal conductivity (k-value) and heat flux of a specimen material at a fixed environmental condition (cold-side temperature, warm-side temperature, vacuum pressure level, and residual gas composition). The apparatus includes an inner vessel for receiving a liquid with a normal boiling point below ambient temperature, such as liquid nitrogen, enclosed within a vacuum chamber. A cold mass assembly, including the upper and lower guard chambers and a middle test vessel, is suspended from a lid of the vacuum canister. Each of the three chambers is filled and vented through a single feedthrough. All fluid and instrumentation feedthroughs are mounted and suspended from a top domed lid to allow easy removal of the cold mass. A lift mechanism allows manipulation of the cold mass assembly and insulation test article.

Fesmire, James E.↗

Current‐Driven Switching of Néel Vector of an Antiferromagnetic Insulator Thin Film

Manipulation of antiferromagnetic (AFM) materials as active elements provides a crucial combination of electrical, thermal, and magnetic properties for spintronics. This study shows how the spin current generated in heavy metal is induced by spin‐orbit torque into an adjacent AFM insulator. The bulk unpinned spins of the AFM layer drive a spin current that is transmitted to the top ferromagnet. This mechanism allows the electrical control of the exchange bias, coercive field, and blocking temperature of the system. Further support is provided by a model calculation that quantitatively describes the effect of the spin current injection into the AFM.

antiferromagnetism↗

Confinement of Lewis Acid–Base Sites by Microporous Silica Layers on Titania for Enhanced Alkanol Dehydration Reactivity

Alkanol dehydration offers a pathway to upgrade biomass-derived short-chain oxygenates into alkenes, essential chemical building blocks widely used in industrial applications. Transition metal oxides with Lewis acid-base site pairs are attractive catalysts due to their high reactivity and cost-effectiveness. This work demonstrates a synthetic pathway to manipulate local environments around active Lewis acid-base pairs in anatase TiO 2 to enhance their reactivity in alkanol dehydration. Microporous SiO 2 layers with an average pore diameter of ~0.6 nm and a controlled thickness of 0.8-33 nm are deposited on anatase TiO 2 powders by using a molecular templated SiO 2 deposition method. The Lewis acid-base strength of accessible Ti-O pairs remains unchanged, as shown by temperature-programmed surface reactions of surface-bound formic acid-derived species and temperature-programmed desorption of pyridine. However, measured alkanol dehydration rates on confined Ti-O pairs are much higher (by up to 7-fold) than those on TiO 2 . The extent of rate enhancements depends on the reactant size and functional group positioning, suggesting that the rate enhancements reflect the interactions between the guest molecules (reactants and transition states) and the surrounding SiO 2 micropore environments. By providing a detailed synthetic procedure to tailor the local environments around active sites in bulk oxides, this approach offers an additional avenue for enhancing catalytic performance.

09 BIOMASS FUELS↗

Anomalous thermal transport in Eshelby twisted van der Waals nanowires

Dislocations in van der Waals (vdW) layered nanomaterials induce strain and structural changes that substantially impact thermal transport. Understanding these effects could enable the manipulation of dislocations for improved thermoelectric and optoelectronic applications, but experimental insights remain limited. Here, in this study, we use synthetic Eshelby twisted vdW GeS nanowires (NWs) with single screw dislocations as a model system to explore the interplay between dislocation-induced structural modifications and lattice thermal conductivity. Our measurements reveal a monoclinic structure stabilized by the dislocation, leading to a substantial drop in thermal conductivity for larger-diameter NWs (70% at room temperature), supported by first-principles calculations. Interestingly, we also find an anomalous enhancement of thermal conductivity with decreasing diameter in twisted NWs, contrary to typical trends in non-twisted GeS NWs. This is attributed to increased conductivity near the NW cores due to compressive strain around the central dislocations, and aligns with a density-functional-theory-informed core–shell model. Our results highlight the critical role of dislocations in thermal conduction, providing fundamental insights for defect and strain engineering in advanced thermal applications.

36 MATERIALS SCIENCE↗

Structural Manipulation of a Zirconocene-Based Porous Coordination Cage Using External and Host–Guest Stimuli

Porous coordination cages (PCCs) constructed from a zirconocene-based cluster have drawn great attention for their high stability and structural tunability. These features have enabled these cages to be utilized for a wide array of applications. Here this work demonstrates the structural flexibility and stimulus-responsive features of two interconvertible zirconocene-based PCCs. The subjects, PCC-20c (capsular) and PCC-20t (tetrahedral), are constructed from the same cluster and ligand but exhibit different shapes and properties. In the synthetic study of the cages, it is found that higher temperatures of synthesis yield PCC-20c in several different crystalline phases while lower temperatures of synthesis yield pure phase PCC-20t. Thermodynamic studies on the interconversion of the two cages show that the conversion from PCC-20t into PCC-20c is an entropically driven process and can be largely affected by the solvent environment. Additionally, the process of PCC-20t/c conversion can be mediated by the counter anions and light irradiation as evidenced by the change in equilibrium constants under these influences. The current studies are conducted to decipher how the PCC-20t/c phase can be controllably synthesized, interconverted, and their properties can be modified under the use of external stimuli: heat, light, and guest molecules.

36 MATERIALS SCIENCE↗

Universal Superconductivity in FeTe and All‐Iron‐Based Ferromagnetic Superconductor Heterostructures

Abstract Ferromagnetism (FM) and superconductivity (SC) are two of the most famous macroscopic quantum phenomena. However, nature normally does not allow SC and FM to coexist without significant degradation. Here, the first fully iron‐based SC/FM heterostructures, composed of Fe(Te,Se) and Fe 3 GeTe 2 , are introduced, and it is shown that this system exhibits both strong FM and high‐temperature SC with an atomically sharp interface. From this study, it is also discovered that minute level of various cationic dopants can drive otherwise non‐superconducting FeTe films into a SC state. This suggests that the ground state of FeTe is so close to the SC state that it can be driven in and out of the SC state with various other perturbations. Altogether, this shows that Fe‐Te‐based heterostructures provide a unique opportunity to manipulate magnetism, superconductivity, and topological physics, paving the way toward new superconducting technologies.

36 MATERIALS SCIENCE↗

A study of in situ reduction of MoO 3 to MoO 2 by X-ray Photoelectron Spectroscopy

Results from X-ray Photoelectron Spectroscopy (XPS) of molybdenum oxide samples are presented to elucidate how Mo (VI) oxide evolves to Mo (IV) oxide upon heating of a MoO 3 sample. XPS data analysis techniques based on manipulation of spectra treated as vectors are shown and allow insights into intermediate phases of Mo oxide which suggest how the original oxide changes under the influence of heat but also supports an interpretation of as-received tetravalent Mo powders as multivalent materials. In particular, several new spectral components were observed and assigned to the Magnéli phase as well as MoO 3 domains that have been modified by the presence of X-rays or temperature. Finally, these assignments comprise a new method of data processing where sample modification is used to inform XPS data interpretation and differ from previous work where the linear relationship of the binding energy of molybdenum oxides has been used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface magnetic anisotropy-mediated spin Hall magnetoresistance and spin Seebeck effects in a YIG/Pt heterostructure

The role of magnon-phonon coupling in the low-temperature behavior of the spin Seebeck effect (SSE) in YIG/Pt has been puzzling for more than a decade. Here, to elucidate the origin of the anomalous peak around 80 K, we investigate the temperature evolution of SSE, spin Hall magnetoresistance (SMR), and magnetic anisotropy in the same YIG/Pt heterostructure. We find that these effects, along with magnetic damping, show the peaks at the same temperature (~80 K). This simultaneous occurrence, where no heat is applied in the case of SMR, rules out the phonon-magnon drag related origin of SSE in the YIG/Pt system. We further show that the intrinsic surface anisotropy behavior in YIG is responsible for controlling the SSE, SMR, and magnetic damping in the YIG/Pt structure. Our findings not only help to understand these effects fundamentally but also provide an effective way for improving them by manipulating the surface magnetic anisotropy for spin caloritronic applications.

36 MATERIALS SCIENCE↗

Spin disorder control of topological spin texture

Abstract Stabilization of topological spin textures in layered magnets has the potential to drive the development of advanced low-dimensional spintronics devices. However, achieving reliable and flexible manipulation of the topological spin textures beyond skyrmion in a two-dimensional magnet system remains challenging. Here, we demonstrate the introduction of magnetic iron atoms between the van der Waals gap of a layered magnet, Fe 3 GaTe 2 , to modify local anisotropic magnetic interactions. Consequently, we present direct observations of the order-disorder skyrmion lattices transition. In addition, non-trivial topological solitons, such as skyrmioniums and skyrmion bags, are realized at room temperature. Our work highlights the influence of random spin control of non-trivial topological spin textures.

36 MATERIALS SCIENCE↗