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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18

In Situ Probing Potassium-ion Intercalation-induced Amorphization in Crystalline Iron Phosphate Cathode Materials

Na-ion and K-ion batteries are promising alternatives for large-scale energy storage applications due to their abundance and low cost. Intercalation of these large ions could cause irreversible structural deformation and partial to complete amorphization in the crystalline electrodes. The designing of new amorphous electrodes is another route to develop electrodes to store these ions reversibly. Lack of understanding of dynamic changes in the amorphous nanostructures during battery operation is the bottleneck for further developments. Here, we report the utilization of in situ digital image correlation and in-operando X-ray diffraction (XRD) techniques to probe dynamic changes in the amorphous phase of iron phosphate during potassium intercalation. In-operando XRD demonstrates amorphization in the electrode’s nanostructure during the first charge/discharge cycle. Additionally, the ex-situ high-resolution transmission electron microscopy further confirms the amorphization after potassium insertion. In situ strain analysis detects the reversible deformation associated with redox reactions in the amorphous phases. Our approach offers new insights on the mechanisms of ion intercalation in the amorphous nanostructures which are highly potent for development of next-generation batteries.

Ozdogru, Bertan↗

Quantitative order-parameter measurement in lattice-mismatched AlInP using precession electron diffraction

Precession electron diffraction (PED) was used to measure the long-range order parameter in lattice-mismatched AlInP epitaxial films under investigation for solid-state-lighting applications. Both double- and single-variant films grown at 620, 650, and 680°C were analyzed in TEM cross-section. PED patterns were acquired in selected-area-diffraction mode through external microscope control using serial acquisition, which allows inline image processing. The integrated peak intensities from experimental patterns were fit using dynamical simulations of diffraction from the ordered domain structures. Included in the structure-factor calculations were mean atomic displacements of the anions (P) due to ordering, which were found by valence-force-field calculations to have a nearly linear dependence on order parameter. A maximum order parameter of S = 0.36 was measured for a double-variant specimen grown at 650°C.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Enabling the High Level Synthesis of Data Analytics Accelerators

Conventional High Level Synthesis (HLS) tools mainly tar- get compute intensive kernels typical of digital signal pro- cessing applications. We are developing techniques and ar- chitectural templates to enable HLS of data analytics appli- cations. These applications are memory intensive, present fine-grained, unpredictable data accesses, and irregular, dy- namic task parallelism. We discuss an architectural tem- plate based around a distributed controller to efficiently ex- ploit thread level parallelism. We present a memory in- terface that supports parallel memory subsystems and en- ables implementing atomic memory operations. We intro- duce a dynamic task scheduling approach to efficiently ex- ecute heavily unbalanced workload. The templates are val- idated by synthesizing queries from the Lehigh University Benchmark (LUBM), a well know SPARQL benchmark.

Data Analytics↗

Complex Intergrowths of Non-Stoichiometric Defect-Structured Hibonite and Al-Rich Spinel in an Allende Ca-Al-Rich Inclusion

Hibonite is a primary ultra-refractory mineral occurring in many Ca-Al-rich inclusions (CAIs) and is predicted to condense as the second major phase from a cooling gas of solar composition. Our previous microstructural studies of hibonite in carbonaceous chondrites revealed its unique microstructures consisting of numerous defects that contain Mg-enriched, wider spinel blocks in stoichiometric hibonite. Han, J. et al. [2 items] demonstrated experimentally that defect-structured hibonites can grow easily in the presence of minor Mg and are kinetically more stable than equilibrium assemblages predicted by thermodynamic calculations. However, a thermo-dynamic vs. structural stability of defect-structured hibonite relative to other early-condensed Al-rich phases such as corundum, grossite, and spinel remains poorly constrained. Here, we present the results of atomic resolution TEM (Transmission Electron Microscopy) imaging of hibonite in a compact Type A CAI in the Allende CV3 chondrite in order to better understand the crystal structure and chemistry of defect-structured hibonite and its associated Al-rich phases, especially non-stoichiometric, Al-rich spinel, in the context of the formation of first refractory solids in the early solar nebula.

Han, J.↗

A Flow-Channel Analysis for the Mars Hopper

The Mars Hopper is an exploratory vehicle designed to fly on Mars using carbon dioxide from the Martian atmosphere as a rocket propellant. The propellent gasses are thermally heated while traversing a radioisotope ther- mal rocket (RTR) engine’s core. This core is comprised of a radioisotope surrounded by a heat capacitive material interspersed with tubes for the propellant to travel through. These tubes, or flow channels, can be manu- factured in various cross-sectional shapes such as a special four-point star or the traditional circle. Analytical heat transfer and computational fluid dynamics (CFD) anal- yses were performed using flow channels with either a circle or a star cross- sectional shape. The nominal total inlet pressure was specified at 2,805,000 Pa; and the outlet pressure was set to 2,785,000 Pa. The CO2 inlet tem- perature was 300 K; and the channel wall was 1200 K. The steady-state CFD simulations computed the smooth-walled star shape’s outlet temper- ature to be 959 K on the finest mesh. The smooth-walled circle’s outlet temperature was 902 K. A circle with a surface roughness specification at 0.01 mm gave 946 K and at 0.1 mm yielded 989 K. The The effects of a slightly varied inlet pressure were also examined. The analytical calculations were based on the mass flow rates computed in the CFD simulations and provided significantly higher outlet temperature results while displaying the same comparison trends. Research relating to the flow channel heat transfer studies was also done. Mathematical methods to geometrically match the cross-sectional areas of the circle and star, along with a square and equilateral triangle, were derived. A Wolfram Mathematica 8 module was programmed to analyze CFD results using Richardson Extrapolation and calculate the grid convergence index (GCI). A Mathematica notebook, also composed, computes and graphs the bulk mean temperature along a flow channel’s length while the user dynam- ically provides the input variables, allowing their effects on the temperature to be more easily observed.

33 ADVANCED PROPULSION SYSTEMS↗

Observation of nanoparticle coalescence during core-shell metallic nanowire growth in colloids via nanoscale imaging

The surface morphology and shape of crystalline nanowires significantly influence their functional properties, including phonon transport, electrocatalytic performance, to name but a few. However, the kinetic pathways driving these morphological changes remain underexplored due to challenges in real-space and real-time imaging at single-particle and atomic resolutions. This study investigates the dynamics of shell (Au, Pd, Pt, Fe, Cu, Ni) deposition on AuAg alloy seed nanowires during core-shell formation. By using chiral/non-chiral seed nanowires, advanced imaging techniques, including liquid-phase transmission electron microscopy (LPTEM), cryogenic TEM, and three-dimensional electron tomography, a three-step deposition process is revealed: heterogeneous nucleation, nanoparticle attachment, and coalescence. It is found that colloidal Ostwald ripening, metal reactivity, and deposition amount modulate nanoparticle size and surface roughness, shaping final morphologies. Noble metal nanoparticles (Au, Ag, Pd, Pt) coalesce with seed nanowire along the 〈111〉 direction, distinct from that of other metals. These findings are consistent across different metals, including Ru, Cu, Fe, and Ni, highlighting the hypothesis of these processes in nanowire formation. These findings enhance traditional crystallographic theories and provide a framework for designing nanowire morphology. Additionally, our imaging techniques may be applied to investigate phenomena like electrodeposition, dendrite growth in batteries, and membrane deformation.

Yang, Dahai↗

Direct observation of atomic-level nucleation and growth processes from an ultrathin metallic glass films

Till date, there have been no direct atomic-level experimental observations of the earliest stages of the nucleation and growth processes of nanocrystals formed by thermally induced crystallization in ultrathin metallic glasses (MGs). Here, we present a study of the crystallization process in atomically thin and highly stable MG films using double spherical aberration-corrected scanning transmission electron microscopy (Cs-TEM). Taking advantage of the stability of MG films with a slow crystallization process and the atomic-level high resolution of Cs-TEM, we observe the formation of the nucleus precursor of nanocrystals formed by atom aggregation followed by concomitant coalescence and stepwise evolution of the shape of the nanocrystals with a monodispersed and separated bimodal size distribution. Molecular dynamics simulation of the atomic motion in the glass film on a rigid amorphous substrate confirms the stepwise evolution processes of atom aggregation, cluster formation, cluster movement on the substrate, and cluster coalescence into larger crystalline particles. Our results might provide a better fundamental understanding of the nucleation and growth processes of nanocrystals in thin MG films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

An Acoustical Comparison of Sub-Scale and Full-Scale Far-Field Measurements for the Reusable Solid Rocket Motor

Recently, members of the Marshall Space Flight Center (MSFC) Fluid Dynamics Branch and Wyle Labs measured far-field acoustic data during a series of three Reusable Solid Rocket Motor (RSRM) horizontal static tests conducted in Promontory, Utah. The test motors included the Technical Evaluation Motor 13 (TEM-13), Flight Verification Motor 2 (FVM-2), and the Flight Simulation Motor 15 (FSM-15). Similar far-field data were collected during horizontal static tests of sub-scale solid rocket motors at MSFC. Far-field acoustical measurements were taken at multiple angles within a circular array centered about the nozzle exit plane, each positioned at a radial distance of 80 nozzle-exit-diameters from the nozzle. This type of measurement configuration is useful for calculating rocket noise characteristics such as those outlined in the NASA SP-8072 "Acoustic Loads Generated by the Propulsion System." Acoustical scaling comparisons are made between the test motors, with particular interest in the Overall Sound Power, Acoustic Efficiency, Non-dimensional Relative Sound Power Spectrum, and Directivity. Since most empirical data in the NASA SP-8072 methodology is derived from small rockets, this investigation provides an opportunity to check the data collapse between a sub-scale and full-scale rocket motor.

Haynes, Jared↗

A Low-Cost and Low-Risk Testbed for Control Design of Launch Vehicles and Landing Systems

This research seeks to bridge the gap between the simulation/theory and the flight-testing phases of control algorithmdesign for launch vehicles (LVs) and landing systems (LSs). Thispaper reviews contemporary testbeds for LV and LS control sys-tem design with an emphasis on reducing costs and risks. Also, anew low-cost and low-risk testbed utilizing a quadcopter, flexibleinverted pendulum, and a hanging pendulum is proposed. It is shown that the planar dynamic response of this proposed testbedcan match the planar dynamic response of an LV. As mission objectives for frequent cislunar and interplanetary travel become more complex, the algorithms that control LVs and LSs need to become more advanced to ensure mission safety and success. These control systems are slow to mature because it is difficult to perform experiments in an environment relevant to the mission in a safe and cost-effective manner. A solution to this problem frequently leveraged in the aviation andsatellite industries involves mimicking the dynamic response ofthe vehicle with a test platform that is low-cost and low-risk.

William J Elke III↗

Investigating Processes of Nanocrystal Formation and Transformation via Liquid Cell TEM

Recent ex situ observations of crystallization in both natural and synthetic systems indicate that the classical models of nucleation and growth are inaccurate. However, in situ observations that can provide direct evidence for alternative models have been lacking due to the limited temporal and spatial resolution of experimental techniques that can observe dynamic processes in a bulk solution. Here we report results from liquid cell transmission electron microscopy studies of nucleation and growth of Au, CaCO3, and iron oxide nanoparticles. We show how these in situ data can be used to obtain direct evidence for the mechanisms underlying nanoparticle crystallization as well as dynamic information that provide constraints on important energetic parameters not available through ex situ methods.

Nielsen, Michael H.↗

Spatially resolved structural order in low-temperature liquid electrolyte

Determining the degree and the spatial extent of structural order in liquids is a grand challenge. Here, we are able to resolve the structural order in a model organic electrolyte of 1 M lithium hexafluorophosphate (LiP 6 ) dissolved in 1:1 (v/v) ethylene carbonate:diethylcarbonate by developing an integrated method of liquid-phase transmission electron microscopy (TEM), cryo-TEM operated at -30°C, four-dimensional scanning TEM, and data analysis based on deep learning. This study reveals the presence of short-range order (SRO) in the high–salt concentration domains of the liquid electrolyte from liquid phase separation at the low temperature. Molecular dynamics simulations suggest the SRO originates from the Li + - (PF 6 - ) n (n > 2) local structural order induced by high LiP 6 salt concentration.

42 ENGINEERING↗

In situ transmission electron microscopy study of the microstructural origins for the electric field-induced phenomena in ferroelectric perovskites

Ferroelectrics are important materials due to their extensive technological applications, such as non-volatile memories, field-effect transistors, ferroelectric tunneling junctions, dielectric capacitors, piezoelectric transducers, sensors and actuators. As is well known, the outstanding dielectric, piezoelectric, and ferroelectric properties of these functional oxides originate from their ferroelectric domain arrangements and the corresponding evolution under external stimuli (e.g. electric field, stress, and temperature). Electric field has been known as the most efficient stimulus to manipulate the ferroelectric domains through polarization switching and alignment. Therefore, direct observation of the dynamic process of electric field-induced domain evolution and crystal structure transformation is of significant importance to understand the microstructural mechanisms for the functional properties of ferroelectrics. In this dissertation, electric field in situ transmission electron microscopy (TEM) technique was employed to monitor the real-time evolution of the domain morphology and crystal structure during various electrical processes: (1) the initial poling process, (2) the electric field reversal process, and (3) the electrical cycling process. Two types of perovskite-structured ceramics, normal ferroelectrics and relaxor ferroelectrics, were used for this investigation. In addition to providing the microscopic insight for some wellaccepted phase transformation rules, discoveries of some new or even unexpected physical phenomena were also demonstrated.

36 MATERIALS SCIENCE↗

Facile hermetic TEM grid preparation for molecular imaging of hydrated biological samples at room temperature

Abstract Although structures of vitrified supramolecular complexes have been determined at near-atomic resolution, elucidating in situ molecular structure in living cells remains a challenge. Here, we report a straightforward liquid cell technique, originally developed for real-time visualization of dynamics at a liquid-gas interface using transmission electron microscopy, to image wet biological samples. Due to the scattering effects from the liquid phase, the micrographs display an amplitude contrast comparable to that observed in negatively stained samples. We succeed in resolving subunits within the protein complex GroEL imaged in a buffer solution at room temperature. Additionally, we capture various stages of virus cell entry, a process for which only sparse structural data exists due to their transient nature. To scrutinize the morphological details further, we used individual particle electron tomography for 3D reconstruction of each virus. These findings showcase this approach potential as an efficient, cost-effective complement to other microscopy technique in addressing biological questions at the molecular level.

59 BASIC BIOLOGICAL SCIENCES↗

Structure, nanomechanics, and dynamics of dispersed surfactant‐free clay nanocomposite films

The current work presents a new approach to achieve high quality dispersion of surfactant‐free nanoclay tactoid particles in sub‐micron thin films despite the absence of organic modifier. Natural Montmorillonite particles, Cloisite, were dispersed in thin films of polycaprolactone (PCL) through a flow coating technique assisted by ultra‐sonication. Wide‐angle X‐ray scattering (WAXS), grazing‐incidence wide‐angle X‐ray scattering (GI‐WAXS), and transmission electron microscopy (TEM) were used to confirm the level of natural clay dispersion down to the level of tactoids (sub‐micron scale stacks of clay sheets). These characterization techniques were carried out in conjunction with an analysis of nanomechanical properties via strain‐induced buckling instability for modulus measurements (SIEBIMM), a high‐throughput technique to characterize thin film mechanical properties. The buckling patterns indicate that the natural clay tactoids separate buckling‐enhancing (high‐modulus) crystalline regions and interconnect buckling‐suppressing amorphous (low‐modulus) regions. Due to the tactoid length scale, the glass transition behavior of the composites as characterized by broadband dielectric relaxation spectroscopy was unmodified by the clay. Likewise, the glass transition temperature, T g , and fragility (slope of relaxation time behavior approaching T g ), remain unaffected, indicating that these dispersed tactoids do not induce pronounced confinement effects on dynamics. POLYM. ENG. SCI., 58:1285–1295, 2018. © 2018 Society of Plastics Engineers

Zhang, Xiao↗

Design Rules for Self-Assembly of 2D Nanocrystal/Metal–Organic Framework Superstructures

Here, we demonstrate the guiding principles behind simple two dimensional self-assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe 3 O 4 ) NCs into a uniform two-dimensional bi-layered superstructure. This self-assembly process can be controlled by the energy of ligand–ligand interactions between surface ligands on Fe 3 O 4 NCs and Zr 6 O 4 (OH) 4 (fumarate) 6 MOF NPs. Scanning transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy and TEM tomography confirm the hierarchical co-assembly of Fe 3 O 4 NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First-principles calculations and event-driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand–surface and ligand–ligand interactions. This study opens a new avenue for design and self-assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self-assembly process, which could be a guide for designing functional materials with desired structure.

74 ATOMIC AND MOLECULAR PHYSICS↗

Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures

Here we demonstrate the guiding principles behind simple two dimensional self-assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe 3 O 4 ) NCs into a uniform two-dimensional bi-layered superstructure. This self-assembly process can be controlled by the energy of ligand–ligand interactions between surface ligands on Fe 3 O 4 NCs and Zr 6 O 4 (OH) 4 (fumarate) 6 MOF NPs. Scanning transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy and TEM tomography confirm the hierarchical co-assembly of Fe 3 O 4 NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First-principles calculations and event-driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand–surface and ligand–ligand interactions. This study opens a new avenue for design and self-assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self-assembly process, which could be a guide for designing functional materials with desired structure.

36 MATERIALS SCIENCE↗

Deformation behavior of crystalline/amorphous Al-Si nanocomposites with nanolaminate or nanofibrous microstructures

Deformation mechanisms in sputter-deposited crystalline Al/amorphous Si nanocomposites with nanolaminate or nanofibrous morphology are characterized by nanoindentation, micropillar compression testing and transmission electron microscopy (TEM). The nanofibrous composite having crystalline Al nanofibers with ~40–50 nm in length and 15–20 nm in diameter embedded in amorphous Si exhibits strain hardening to a maximum flow stress of 2.9 GPa and no shear band (SB) formation in compression up to plastic strain exceeding 24%. On the other hand, nanolaminate composite that is composed of 80 nm crystalline Al layers and 20 nm amorphous Si layers exhibits catastrophic SBs starting at plastic strains in the range of 5–10%. Cross-sectional TEM of the deformed samples reveals a high density of stacking faults and twin boundaries in Al nanofibers and no microshear bands in the nanofibrous composite, suggesting plastic deformation in amorphous Si phase and crystalline Al nanofibers. Further, molecular dynamics simulations revealed that the plastic deformation in amorphous Si phase in the cosputtered films could be favored by the decrease in flow strength of amorphous Si with increasing Al solute concentration trapped in Si.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of Protein-Water Interface in the Stacking Interactions of Granum Thylakoid Membranes—As Revealed by the Effects of Hofmeister Salts

The thylakoid membranes of vascular plants are differentiated into stacked granum and unstacked stroma regions. The formation of grana is triggered by the macrodomain formation of photosystem II and light-harvesting complex II (PSII-LHCII) and thus their lateral segregation from the photosystem I—light-harvesting complex I (PSI-LHCI) super-complexes and the ATP-synthase; which is then stabilized by stacking interactions of the adjacent PSII-LHCII enriched regions of the thylakoid membranes. The self-assembly and dynamics of this highly organized membrane system and the nature of forces acting between the PSII-LHCII macrodomains are not well understood. By using circular dichroism (CD) spectroscopy, small-angle neutron scattering (SANS) and transmission electron microscopy (TEM), we investigated the effects of Hofmeister salts on the organization of pigment-protein complexes and on the ultrastructure of thylakoid membranes. We found that the kosmotropic agent (NH 4 ) 2 SO 4 and the Hofmeister-neutral NaCl, up to 2 M concentrations, hardly affected the macro-organization of the protein complexes and the membrane ultrastructure. In contrast, chaotropic salts, NaClO 4 , and NaSCN destroyed the mesoscopic structures, the multilamellar organization of the thylakoid membranes and the chiral macrodomains of the protein complexes but without noticeably affecting the short-range, pigment-pigment excitonic interactions. Comparison of the concentration- and time-dependences of SANS, TEM and CD parameters revealed the main steps of the disassembly of grana in the presence of chaotropes. It begins with a rapid diminishment of the long-range periodic order of the grana membranes, apparently due to an increased stacking disorder of the thylakoid membranes, as reflected by SANS experiments. SANS measurements also allowed discrimination between the cationic and anionic effects—in stacking and disorder, respectively. This step is followed by a somewhat slower disorganization of the TEM ultrastructure, due to the gradual loss of stacked membrane pairs. Occurring last is the stepwise decrease and disappearance of the long-range chiral order of the protein complexes, the rate of which was faster in LHCII-deficient membranes. These data are interpreted in terms of a theory, from our laboratory, according to which Hofmeister salts primarily affect the hydrophylic-hydrophobic interactions of proteins, and the stroma-exposed regions of the intrinsic membrane proteins, in particular—pointing to the role of protein-water interface in the stacking interactions of granum thylakoid membranes.

59 BASIC BIOLOGICAL SCIENCES↗