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At least 181 records · Page 10

Practical Applications of Cosmic Ray Science: Spacecraft, Aircraft, Ground-Based Computation and Control Systems, Exploration, and Human Health and Safety

In this presentation a review of galactic cosmic ray (GCR) effects on microelectronic systems and human health and safety is given. The methods used to evaluate and mitigate unwanted cosmic ray effects in ground-based, atmospheric flight, and space flight environments are also reviewed. However not all GCR effects are undesirable. We will also briefly review how observation and analysis of GCR interactions with planetary atmospheres and surfaces and reveal important compositional and geophysical data on earth and elsewhere. About 1000 GCR particles enter every square meter of Earth’s upper atmosphere every second, roughly the same number striking every square meter of the International Space Station (ISS) and every other low- Earth orbit spacecraft. GCR particles are high energy ionized atomic nuclei (90% protons, 9% alpha particles, 1% heavier nuclei) traveling very close to the speed of light. The GCR particle flux is even higher in interplanetary space because the geomagnetic field provides some limited magnetic shielding. Collisions of GCR particles with atomic nuclei in planetary atmospheres and/or regolith as well as spacecraft materials produce nuclear reactions and energetic/highly penetrating secondary particle showers. Three twentieth century technology developments have driven an ongoing evolution of basic cosmic ray science into a set of practical engineering tools needed to design, test, and verify the safety and reliability of modern complex technological systems and assess effects on human health and safety effects. The key technology developments are: 1) high altitude commercial and military aircraft; 2) manned and unmanned spacecraft; and 3) increasingly complex and sensitive solid state micro-electronics systems. Space and geophysical exploration needs drove the development of the instruments and analytical tools needed to recover compositional and structural data from GCR induced nuclear reactions and secondary particle showers. Finally, the possible role of GCR secondary particle showers in addressing an important homeland security problem, finding nuclear contraband and weapons, will be briefly reviewed.

Koontz, Steve↗

Low-Temperature Production of Cosmic Grains Analogs From Gas-Phase Molecular Precursors with the NASA Ames' COSmIC Facility

Complex carbon molecules and ions are ubiquitous in space and form the building blocks of carbonaceous cosmic dust grains, ultimately contributing to the formation of planets. Here, we report the first experimental investigations of the low temperature chemical pathways leading to the production of cosmic grain analogs from gas phase molecular precursors in order to better understand the evolution of cosmic carbon. The experiments were performed using the COsmic SImulation Chamber (COSmIC) to generate and characterize grains formed from gas phase precursors under controlled conditions representative of astrophysical environments [1]. Using COSmIC, it is possible to investigate the evolution of cosmic carbon from the formation of neutral and ionized gas phase hydrocarbons and PAHs [2], to carbon grains [3, 4]. This is achieved by using a discharge nozzle to (1) produce an adiabatic jet expansion and cool down Ar-hydrocarbon/PAH gas mixtures to astrophysically relevant temperature (150 K) before inducing chemistry by generating a plasma discharge in the stream of the expansion. This plasma-induced chemistry results in the formation of complex molecules and solid particles, analogs of cosmic grains. Solid grains are produced in-situ in the plasma expansion, carried by the accelerated gas in the expansion, and collected on substrates placed a few centimeters downstream of the electrodes. The results of a preliminary solid phase ex-situ analysis of cosmic grain analogs produced at low temperature in COSmIC from gas mixtures including molecular precursors of cosmic carbon grains, i.e., such as CH4 and C2H2 found in circumstellar ejecta of late C stars [3] as well as PAHs ubiquitously detected in IR emission bands seen in galactic and extragalactic environments [4] will be discussed. Scanning Electron Microscopy imaging was used to provide insight on the morphology and growth structure of the grains produced in COSmIC, and to investigate how the precursors used to produce the grains affect these parameters [3]. Laser desorption mass spectrometry was used to identify the molecules making up the main structures within the condensed grains [4]. NIR to FIR optical properties are characterized to provide critical information (functional groups, optical constants) to the scientific community, for use in radiative transfer models in particular, and to help decipher and enhance the return data from space observations.

F. Salama↗

Cold Metal Transfer (CMT) Wire-Arc Additive Manufacturing (WAAM)

Aluminum has been identified as a compound within regolith and is likely to become a core component of our infrastructure on the lunar surface as in-situ resource utilization (ISRU) capabilities are advanced Large-scale components, outfitting, and repairs of aluminum materials can be fabricated with robotic wire arc additive manufacturing (WAAM) in order to inhabit the moon’s surface long term WAAM is a high value process for lunar advanced manufacturing as it does not require special containment to reduce explosion hazards such as powder-based additive processes and feedstock The welding process of cold metal transfer (CMT) is a relatively new variation of gas metal arc welding (GMAW, also known as MIG) that relies on the detection of a short circuit in the welding process to control the deposition droplet action, resulting in lower heat input and splatter compared to conventional MIG welding The past year was spent developing the CMT-WAAM process for aluminum materials, tested specialty feedstock, tested within the high vacuum environment, and advanced the MSFC capability to perform complex toolpathing from solid models Upcoming and future work includes large depositions working towards material certification for multiple feedstocks, in-situ monitoring, work to use recycled materials for the AM feedstock, and the design and fabrication of a parabolic flight experiment payload.

cold metal transfer↗

Launch Complex 39A, SWMU 008 2023 Long-Term Monitoring Report Kennedy Space Center, Florida

The 2023 Long-Term Monitoring (LTM) Report (LTMR) presents the annual and semi-annual groundwater monitoring results for Launch Complex 39A (LC39A), Solid Waste Management Unit (SWMU) 008, at Kennedy Space Center (KSC), Florida. The reporting period covered under this LTMR is from January to December 2023, and represents the first year of site-wide monitoring following Air Sparge (AS) system shutdown at the end of 2022. AS system operation at LC39A began operation in 2015. The AS system consisted of a total of 173 AS wells ranging in depth from 11 to 37 feet below land surface. The overall remedial objective for the AS Interim Measure was to actively decrease concentrations of COCs to less than their respective Florida Department of Environmental Protection Natural Attenuation Default Concentrations, so that LC39A can transition into an LTM program. This objective was achieved in 2022, with 2023 marking Year 1 of the LTM program to monitor the residual groundwater plume. VOC results indicate that COC concentrations have continued to decrease or stabilize, with no rebound observed since AS system shutdown. Vinyl chloride was the only COC detected above its GCTL, with the highest concentration detected at 8.0 μg/L. PFAS results detected 15 different PFAS compounds (out of 32 analyzed) between the six monitoring wells sampled. Two PFAS compounds, perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), currently have FDEP Provisional GCTLs of 70 nanograms per liter (ng/L). PFOS was detected in one of the six samples above the FDEP Provisional GCTL at a concentration of 200 ng/L. PFOA was not detected above the FDEP Provisional GCTL in any of the six samples. PFOS and PFOA also currently have United States Environmental Protection Agency (USEPA) Maximum Contaminant Levels (MCLs) of 4 ng/L. PFOS was detected in all six samples above the USEPA MCL. PFOA was detected in three of the six samples above the USEPA MCL. Three other PFAS compounds, perfluorohexanesulfonic acid (PFHxS), perfluoro-n-nonanoic acid (PFNA), and hexafluoropropylene oxide dimer acid (GenX), currently have USEPA MCLs of 10 ng/L. PFHxS, PFNA, and GenX were not detected at concentrations greater than their respective USEPA MCLs in any of the six wells. Additional PFAS sampling will occur as part of a PFAS Site Assessment to be conducted in the future. Based on Year 1 LC39A LTM results, recommendations for 2024 are to continue with the second year of LTM in 2024 with the same monitoring well network as Year 1 (18 wells). The three wells that were on a semi-annual schedule will transition to an annual schedule to align with the remaining wells. The next annual event is scheduled for May 2024. The three wells that were found to be inadvertently destroyed will be properly abandoned and a replacement well in the vicinity of former monitoring well 21ST-MW0030I will be installed. This new well will be added to the LTM sampling plan upon installation.

Deborah M. Wilson↗

Uranyl Naphthylsalophen and Pyrasal Complexes: Oxo Ligands Acting as Hydrogen Bond Acceptors in the Solid State

Uranium is most stable when it is exposed to oxygen or water in its +6 oxidation state as the uranyl (UO 2 2+ ) ion. This ion is subsequently particularly stable and very resistant to functionalization due to the inverse trans effect. Uranyl oxo ligands are typically not considered good hydrogen bond acceptors due to their weak Lewis basicity; however, the ligands bound in the equatorial plane greatly affect the strength of the oxo ligands’ hydrogen bonding. Here, in this work, new naphthylsalophen and pyrasal complexes of uranium were synthesized and crystallized for characterization in the solid state. The bond lengths and angles of the uranyl ion and the ligand conformation are compared. In the solid state, one of the pyrasal complexes showed a hydrogen bond directly from a water molecule to the uranyl oxo ligand, which resulted in an asymmetric lengthening of the U–O yl bonds from 1.789 to 1.862 Å and 1.784 to 1.844 Å.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excitons: Energetics and spatiotemporal dynamics

The concept of an exciton as a quasiparticle that represents collective excited states was originally adapted from solid-state physics and has been successfully applied to molecular aggregates by relying on the well-established limits of the Wannier exciton and the Frenkel exciton. However, the study of excitons in more complex chemical systems and solid materials over the past two decades has made it clear that simple concepts based on Wannier or Frenkel excitons are not sufficient to describe detailed excitonic behavior, especially in nano-structured solid materials, multichromophoric macromolecules, and complex molecular aggregates. In addition, important effects such as vibronic coupling, the influence of charge-transfer (CT) components, spin-state interconversion, and electronic correlation, which had long been studied but not fully understood, have turned out to play a central role in many systems. This has motivated new experimental approaches and theoretical studies of increasing sophistication. This article provides an overview of works addressing these issues that were published for A Special Topic of the Journal of Chemical Physics on ``Excitons: Energetics and spatio-temporal dynamics" and discusses their implications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid‐State Reaction Heterogeneity During Calcination of Lithium‐Ion Battery Cathode

Abstract During solid‐state calcination, with increasing temperature, materials undergo complex phase transitions with heterogeneous solid‐state reactions and mass transport. Precise control of the calcination chemistry is therefore crucial for synthesizing state‐of‐the‐art Ni‐rich layered oxides (LiNi 1‐x‐y Co x Mn y O 2 , NRNCM) as cathode materials for lithium‐ion batteries. Although the battery performance depends on the chemical heterogeneity during NRNCM calcination, it has not yet been elucidated. Herein, through synchrotron‐based X‐ray, mass spectrometry microscopy, and structural analyses, it is revealed that the temperature‐dependent reaction kinetics, the diffusivity of solid‐state lithium sources, and the ambient oxygen control the local chemical compositions of the reaction intermediates within a calcined particle. Additionally, it is found that the variations in the reducing power of the transition metals (i.e., Ni, Co, and Mn) determine the local structures at the nanoscale. The investigation of the reaction mechanism via imaging analysis provides valuable information for tuning the calcination chemistry and developing high‐energy/power density lithium‐ion batteries.

Chemistry↗

Multiscale investigations of europium(III) complexation with tetra- n -octyl diglycolamide confined in porous solid supports

The microscopic, short-range coordination environments and mesoscopic, long-range structures of Eu 3+ contacted with tetra-n-octyl diglycolamide (TODGA) confined on ordered mesoporous carbon (OMC) nanoparticles and Amberchrom CG 71 resin were probed using Eu L 3 -edge extended X ray absorption fine structure (EXAFS) as well as small-angle and wide-angle X ray scattering, SAXS and WAXS, respectively. A homoleptic Eu(TODGA) 3 3+ coordination complex typical of liquid-liquid extraction (LLE) chemistry is present under low Eu 3+ loading conditions on both solid supports. Deviations from this traditional structure motif appear at hyperstoichiometric Eu 3+ loadings, above the 1:3 Eu 3+ to TODGA mole ratio. Microcrystalline-like domains with multinuclear Eu speciation are templated by use of these high Eu 3+ loading conditions with the functionalized OMC materials, highlighting a major departure of liquid-solid extraction chromatography (EXC) from the coordination chemistry of LLE. No such long-range spatial coherence was observed for analogous polyacrylic resin materials. Furthermore, these results demonstrate both the similarities and differences between multiscale structures in LLE and EXC, underscoring the opportunities for improved separation techniques based on solid supports with long-range spatial coherence (e.g., OMC systems) and without it (e.g., resin materials). Since crystallization was the first approach to adjacent lanthanide separations, the prospect of templating microcrystalline TODGA-lanthanide complexes that are otherwise not prone to crystallization by use of OMC nanoparticles represents a new entry to addressing long-standing issues in purification by liquid-solid phase separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Entropy-driven melting point depression in fcc HEAs

High Entropy Alloys (HEAs) are an increasingly dominant alloy design paradigm. The premise of entropic stabilization of single-phase alloys has motivated much of the research on HEAs. Chemical complexity may indeed help stabilize single alloy phases relative to other lower-entropy competing solid phases. Paradoxically, this complexity may de-stabilize these alloys against the liquid phase, potentially limiting the application space of HEAs at elevated temperatures. In this work, we carry out a comprehensive investigation of the phase stability in the fcc CoCrFeMnNiV-Al HEA space using a state of the art CALPHAD database. By using modern visualization techniques and statistical analysis we examine the trade-off between chemical complexity and stability against the liquid state and identify a potentially difficult to overcome barrier for development of high temperature alloys, at least within the conventional fcc HEA space. Here, limited experimental data seem to be consistent with this analysis.

36 MATERIALS SCIENCE↗

Lithium-Based High Energy Density Flow Batteries

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Bugga, Ratnakumar V.↗

Synthesis and characterization of the rare-earth chloride complexes with N,N,N',N' -tetramethylmalonamide

Exploration of the solid-state chemistry of the f-elements and their coordination chemistry can assist in understanding the speciation of these elements in solution, which, in turn, can aid in the interpretation of their chemical behavior in complex liquid-liquid separations. Within these separation processes, malonamides are common organic extractants that are used for complexing both lanthanides and actinides, thus it is relevant to understand the malonamide ligand complexation under various conditions. In this work, we investigate solid-state complexes of the rare-earth chlorides with N,N,N',N' -tetramethylmalonamide (TMMA) across the entire lanthanide series. Here, we isolated two structural families of compounds Ln(TMMA) 2 Cl 3 Ln = La–Dy and [Ln(TMMA) 2 (H 2 O) 4 ]Cl 3 • x H 2 O x = 0,4 Ln = Ho–Lu, showing differences in chloride coordination from the inner-sphere complex for early lanthanides to outer-sphere for the late lanthanides. Both structural series were additionally analyzed by both IR and Raman spectroscopy confirming similarities in malonamide ligand coordination modes, while showing differences in vibrational features associated with chloride and aqua ligand coordination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the Limits of Biological Complexity Amenable to Studies by Incoherent Neutron Spectroscopy

The wavelengths of neutrons available at neutron scattering facilities are comparable with intra- and inter-molecular distances, while their energies are comparable with molecular vibrational energies, making such neutrons highly suitable for studies of molecular-level dynamics. The unmistakable trend in neutron spectroscopy has been towards measurements of systems of greater complexity. Several decades of studies of dynamics using neutron scattering have witnessed a progression from measurements of solids to liquids to protein complexes and biomembranes, which may exhibit properties characteristic of both solids and liquids. Over the last two decades, the frontier of complexity amenable to neutron spectroscopy studies has reached the level of cells. Considering this a baseline for neutron spectroscopy of systems of the utmost biological complexity, we briefly review what has been learned to date from neutron scattering studies at the cellular level and then discuss in more detail the recent strides into neutron spectroscopy of tissues and whole multicellular organisms.

59 BASIC BIOLOGICAL SCIENCES↗

Understanding effects of chemical complexity on helium bubble formation in Ni-based concentrated solid solution alloys based on elemental segregation measurements

Here, helium bubble formation and swelling were systematically studied in Ni-based concentrated solid solution alloys containing different numbers and types of elements. Our microscopy analysis showed that although increasing the alloy chemical complexity helps suppress bubble formation in general, there is no monotonic relationship between the bubble growth rate and the number of alloying elements. Certain elements (e.g., Fe and Pd) are more effective in suppressing bubble growth than others (e.g., Cr and Mn). Atom probe tomography was applied to accurately measure elemental segregation around bubbles, revealing unique effects of certain alloying elements on vacancy migration towards bubbles. More specifically, the high vacancy mobility via Cr sites leads to a large vacancy flux and an increased bubble size, while the high degree of atomic size mismatch introduced by Pd helps deflect vacancy flow away from bubbles and decrease the amount of swelling. The effects identified in this study provide new strategies to design concentrated solid solutions with superior resistance to swelling.

36 MATERIALS SCIENCE↗

Method—Using Microelectrodes to Explore Solid Polymer Electrolytes

Solid polymer electrolytes are an emerging technology in electrochemistry driven by their use in energy applications such as fuel cells, electrolyzers, and solid-state batteries. Compared to traditional liquid electrolytes, solid polymer electrolytes provide safer, cheaper, and potentially improved device performance. However, there is a lack of standard experimental methods for studying solid electrolytes. Microelectrodes have inherent benefits capable of filling this experimental gap due primarily to their integration into model electrochemical cells with solid electrolytes that represent complex interfaces, enabling additional insight into reaction processes. In this tutorial review, we explore the use of microelectrodes to study solid polymer electrolytes, beginning with a brief history of the field including common experimental cell designs and their benefits and drawbacks. Methods of evaluating essential kinetic and mass-transport parameters are then examined. In addition, the key studies of the past 30 years utilizing microelectrode cells and solid polymer electrolytes are summarized, with important results highlighted and compared. Finally, future studies of solid polymer electrolytes with microelectrodes and potential new avenues of research are commented on.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Convective influence on the stability of a cylindrical solid-liquid interface

Experiments in which a long vertical, heated wire is surrounded by concentric annuli of a melt and its crystalline solid show that the convection state changes from a stable unicell surrounded by a stationary cylindrical solid-liquid interface, to a complex time-dependent flow surrounded by a rotating, helical solid-liquid interface. This transition occurs at a Grashof number of approximately 150, which is an order of magnitude less than the critical Grashof number calculated for a liquid annulus surrounded by rigid walls. A linear stability analysis has been carried out for an infinitely tall vertical annulus. When the deformable nature of the crystal-melt interface is taken into account in the boundary conditions, two new modes of instability arise. The most dangerous mode is asymmetrical and corresponds to helical waves travelling vertically upwards. The critical Grashof number and the scaling properties of the eigenstate agree with experiments. The results clearly demonstrate the coupling of convection with crystal-melt interfacial instabilities.

Fang, Q. T.↗

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

Abstract High‐energy X‐ray scattering and pair distribution function analysis (HEXS/PDF) is a powerful method to reveal the structure of materials lacking long‐range order, but is underutilized for molecular complexes in solution. We demonstrate the application of HEXS/PDF with 0.26 Å resolution to uncover the solution structure of five bimetallic Cu I /Ru II /Os II complexes. HEXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metal⋅⋅⋅metal distances separated by over 12 Å. The metal⋅⋅⋅metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state. This work presents the first example of observing sub‐Ångström conformational differences by direct comparison of solution phase and solid‐state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.

Xie, Zhu‐Lin↗

Formation of complex impact craters - Evidence from Mars and other planets

An analysis of the depth vs diameter data of Arthur (1980), is given along with geomorphic data for 73 Martian craters. The implications for the formation of complex impact craters on solid planets is discussed. The analysis integrates detailed morphological observations on planetary craters with geologic data from terrestrial meteorite and explosion craters. The simple to complex transition for impact craters on Mars appears at diameters in the range of 3 to 8 km. Five features appear sequentially with increasing crater size, flat floors, central peaks and shallower depths, scalloped rims, and terraced walls. This order suggests that a shallow depth of excavation and a rebound mechanism have produced the central peaks, not centripetal collapse and deep sliding. Simple craters are relatively uniform in shape from planet to planet, but complex craters vary considerably. Both the average onset diameter for complex impact craters on Mars and the average depth of complex craters vary inversely with gravitational acceleration on four planets.

Pike, R. J.↗

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

High-energy X-ray scattering and pair distribution function analysis (HEXS/PDF) is a powerful method to reveal the structure of materials lacking long-range order, but is underutilized for molecular complexes in solution. Here we demonstrate the application of HEXS/PDF with 0.26 Å resolution to uncover the solution structure of five bimetallic Cu I /Ru II /Os II complexes. HEXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metal...metal distances separated by over 12 Å. The metal…metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state. This work presents the first example of observing sub-Ångström conformational differences by direct comparison of solution phase and solid-state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗