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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Building a Framework to Understand Transition Metals' Behavior in Euxinic Conditions (Final Technical Report)

This project focuses first and foremost on metal sulfide geochemistry and mineralogy as controlled by a complex matrix of environmental factors. The principal investigator’s group aim to illuminate the metal-sulfide reaction mechanisms, rates, and pathways through systematic experimentation and data collection and analyzing the relationships between the characteristics of the produced metal sulfide solid-phase/aqueous complexes and the environmental factors. This understanding is essential for obtaining a full picture of the complex cycling patterns of single or multi metal species in sulfidic environments ranging from deep-see basins, hydrothermal vents, inland seas, terrestrial water bodies, to engineered remediation systems. The specific goal of this past project was to illuminate the reaction mechanisms and kinetics of metal anions and sulfide in mixed metal cation-metal anion-sulfide systems under various aqueous conditions (which resembled a range of naturally occurring euxinic settings). For the period of this contract, we investigated the molybdenum-iron-sulfide system, with an emphasis on the conditions that caused solid phase formation. We focused on quantifying the mobility/sequestration of molybdenum under each experimental condition and identified the changes of valence states for each involved element (i.e., Mo, Fe, and S) in the precipitate. We also proposed pathways for the electron transfer that occurred in aqueous chemistry. The major analytical tools used for this study include UV-visible light spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and synchrotron-based X-ray absorption spectroscopy (access gained through facility proposals to the Canadian Light Source). The biggest finding of this project was that besides pH, the iron-sulfur chemistry has a dominant control of the thiolation kinetics and subsequent reduction of Mo(VI), which are likely prerequisites of molybdenum sequestration in anoxic conditions. The results have been written up as manuscript by the end of this project (see Phillips et al.). The experimental results of this project may be critical for advancing our understanding of (1) basic chemistry involving transition metals and reduced sulfur species, (2) the validity of certain geochemical proxies, and (3) the stability and evolution of euxinic geochemical environments. It is noted that the basic results obtained through this project also have implications for Mo-S cluster-based catalyst development in inorganic chemistry and materials sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Comparison of methods to derive infrared optical constants for organic materials for optical modeling

Reflectance spectroscopy, especially at infrared wavelengths, is often used for contact, standoff, and remote sensing of solid materials. The reflectance spectra of solids, however, are complex, relying on many factors, even for the same material. Such phenomena can be modeled if the optical constants as a function of wavelength or wavenumber, n(?) and k(?), are known. Methods to measure the optical constants of solids, however, are challenging, particularly for powdered materials. For powdered materials, a pressed pellet of the neat material is often used when a crystalline specimen is not available. In this work, three techniques, including ellipsometry, single-angle reflectance and KBr transmission spectroscopy, are applied to an organic material, acetaminophen, for comparison, and the effects on the modeled spectra are shown.

ellipsometry, infrared (IR) spectroscopy, FTIR, hy↗
NASA NTRS1992

Secondary Li battery incorporating 12-Crown-4 ether

A rechargeable lithium battery which utilizes a polyethylene oxide (PEO) solid polymeric electrolyte complexed with a lithium salt is disclosed. The conductivity is increased an order of magnitude and interfacial charge transfer resistance is substantially decreased by incorporating a minor amount of 12-Crown-4 ether in the PEO-lithium salt solid electrolyte film. Batteries containing the improved electrolyte permit operation at a lower temperature with improved efficiency.

Nagasubramanian, Ganesan↗
DOE OSTI2025

Similar but Different: Structural and Spectroscopic Characterization of Series of Neodymium, Europium, Americium, and Curium Coordination Complexes

Series of curium, americium, europium, and neodymium complexes with five different polyoxometalate (POM) ligands were structurally and spectroscopically characterized: Na x Cs y H z [M(XW 11 O 39 ) 2 ]· n H 2 O, where M = Nd 3+ , Eu 3+ , Am 3+ , or Cm 3+ and X = B 3+ , Ga 3+ , Si 4+ , Ge 4+ , or P 5+ . This first “serial approach” on transplutonium chemistry was allowed by minimizing the amount of f-element needed per synthesis down to ∼10 μg. This offers a unique opportunity to contrast structural and spectroscopic properties of trivalent actinide with those of lanthanide compounds under identical conditions. The results showcase that although actinide(III) and lanthanide(III) can make isostructural complexes, their solid-state coordination chemistries deviate significantly. The curium and americium compounds were found to be more uniform than their europium and neodymium counterparts, respectively. The particular symmetry of the Cm-POMs also enables the observation of rarely seen emission bands, which hints at vibronic coupling or new emissive pathways. Additionally, the Cm-POM and Eu-POM complexes were characterized via steady-state and time-resolved excitation and emission spectroscopy in solutions containing five different counterions (Li + , Na + , K + , Rb + , or Cs + ), representing 50 combinations of alkali/[M III (XW 11 ) 2 ] n − complexes. The Cm-POMs respond to the alkali counterions by improving symmetry from Li + to Cs + , while the Eu-POMs do the opposite. The luminescence lifetimes of the Cm-POMs also depart from the ideal Kimura equation. Finally, this study provides a rare, and perhaps the most comprehensive, experimental data set comparing heavy actinides and lanthanides via single crystal XRD plus, solution-state, solid-state, and time-resolved emission spectroscopy and demonstrates that lanthanides are only a coarse approximation for actinide elements.

chemical structure↗
NASA NTRS2014

Using SpaceClaim/TD Direct for Modeling Components with Complex Geometries for the Thermal Desktop-Based Advanced Stirling Radioisotope Generator Model

SpaceClaim/TD Direct has been used extensively in the development of the Advanced Stirling Radioisotope Generator (ASRG) thermal model. This paper outlines the workflow for that aspect of the task and includes proposed best practices and lessons learned. The ASRG thermal model was developed to predict component temperatures and power output and to provide insight into the prime contractors thermal modeling efforts. The insulation blocks, heat collectors, and cold side adapter flanges (CSAFs) were modeled with this approach. The model was constructed using mostly TD finite difference (FD) surfaces solids. However, some complex geometry could not be reproduced with TD primitives while maintaining the desired degree of geometric fidelity. Using SpaceClaim permitted the import of original CAD files and enabled the defeaturing repair of those geometries. TD Direct (a SpaceClaim add-on from CRTech) adds features that allowed the mark-up of that geometry. These so-called mark-ups control how finite element (FE) meshes were generated and allowed the tagging of features (e.g. edges, solids, surfaces). These tags represent parameters that include: submodels, material properties, material orienters, optical properties, and radiation analysis groups. TD aliases were used for most tags to allow analysis to be performed with a variety of parameter values. Domain-tags were also attached to individual and groups of surfaces and solids to allow them to be used later within TD to populate objects like, for example, heaters and contactors. These tools allow the user to make changes to the geometry in SpaceClaim and then easily synchronize the mesh in TD without having to redefine these objects each time as one would if using TD Mesher.The use of SpaceClaim/TD Direct has helped simplify the process for importing existing geometries and in the creation of high fidelity FE meshes to represent complex parts. It has also saved time and effort in the subsequent analysis.

Power Systems↗
NASA NTRS2012

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

In this paper we review the discovery of cosmic ray effects on the performance and reliability of microelectronic systems as well as on human health and safety, as well as the development of the engineering and health science tools used to evaluate and mitigate cosmic ray effects in earth surface, atmospheric flight, and space flight environments. Three twentieth century technological developments, 1) high altitude commercial and military aircraft; 2) manned and unmanned spacecraft; and 3) increasingly complex and sensitive solid state micro-electronics systems, have driven an ongoing evolution of basic cosmic ray science into a set of practical engineering tools (e.g. ground based test methods as well as high energy particle transport and reaction codes) needed to design, test, and verify the safety and reliability of modern complex electronic systems as well as effects on human health and safety. The effects of primary cosmic ray particles, and secondary particle showers produced by nuclear reactions with spacecraft materials, can determine the design and verification processes (as well as the total dollar cost) for manned and unmanned spacecraft avionics systems. Similar considerations apply to commercial and military aircraft operating at high latitudes and altitudes near the atmospheric Pfotzer maximum. Even ground based computational and controls systems can be negatively affected by secondary particle showers at the Earth's surface, especially if the net target area of the sensitive electronic system components is large. Accumulation of both primary cosmic ray and secondary cosmic ray induced particle shower radiation dose is an important health and safety consideration for commercial or military air crews operating at high altitude/latitude and is also one of the most important factors presently limiting manned space flight operations beyond low-Earth orbit (LEO).

Atwell, William↗
DOE OSTI2023

Tailoring Chemical Absorption-Precipitation to Lower the Regeneration Energy of a CO 2 Capture Solvent

Solvent-based CO 2 capture consumes significant amounts of energy for solvent regeneration. To improve energy efficiency, this study investigates CO 2 fixation in a solid form through solvation, followed by ionic self-assembly-aided precipitation. Based on the hypothesis that CO 3 2- ions may bind with monovalent metal ions, we introduced Na + into an aqueous hexane-1,6-diamine solution where CO 2 forms carbamate and bicarbonate. Then, Na + ions in the solvent act as a seed for ionic self-assembly with diamine carbamate to form an intermediate ionic complex. The recurring chemical reactions lead to the formation of an ionic solid from a mixture of organic carbamate/carbonate and inorganic sodium bicarbonate (NaHCO 3 ), which can be easily removed from the aqueous solvent through sedimentation or centrifugation and heated to release the captured CO 2 . Mild-temperature heating of the solids at 80–150 °C causes decomposition of the solid CO 2 -diamine-Na molecular aggregates and discharge of CO 2 . This sorbent regeneration process requires 6.5–8.6 GJ/t CO 2 . It was also found that the organic carbamate/carbonate solid, without NaHCO 3 , contains a significant amount of CO 2 , up to 6.2 mmol CO 2 /g-sorbent, requiring as low as 2.9–5.8 GJ/t CO 2 . In conclusion, molecular dynamic simulations support the hypothesis of using Na + to form relatively less stable, yet sufficiently solid, complexes for the least energy-intensive recovery of diamine solvents compared to bivalent carbonate–forming ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structure and properties of bottlebrush polyelectrolyte complexes

Abstract Structural variation of polyelectrolytes has been shown to play an important role in altering polyelectrolyte complex (PEC) properties in recent years. However, molecular‐level details such as polyelectrolyte architecture remain underdeveloped. Here, we use a combination of ring‐opening metathesis polymerization (ROMP), atom‐transfer radical polymerization (ATRP), and postpolymerization reactions to create densely branched bottlebrushes of poly(dimethylamino ethyl methcacrylate) and poly(tert‐butyl methacrylate) with high molecular weights (MDa), which we then convert into fully charged and densely branched bottlebrushes of poly(trimethylaminoethyl methacrylate) (PTMAEMA) and poly(methacrylic acid) (PAA). We investigate the structure and properties of bottlebrush polyelectrolyte complexes (BPECs) using optical microscopy, rheology, cryogenic transmission electron microscopy (Cryo‐TEM), and small‐angle X‐ray scattering (SAXS). Bottlebrush polyelectrolyte complexes are white solids, which exhibit gel‐like mechanical properties, which we attribute to sidechain interpenetration. Using a combination of Cryo‐TEM and SAXS, we are able to outline the structural development of BPECs, detailing how the network topology, sidechain conformation, and interdigitation spacing changes as a function of salt. Our results provide a foundation for further exploration of branched architectures within polyelectrolyte complexation.

Polymer Science↗
DOE OSTI2020

Defect evolution in Ni and solid-solution alloys of NiFe and NiFeCoCr under ion irradiation at 16 and 300 K

Single-phase concentrated solid-solution alloys (SP-CSAs) have shown unique chemical complexity at the levels of electrons and atoms, and their defect evolution is expected to be different from conventional dilute alloys. Single crystals of Ni, NiFe and NiFeCoCr are chosen as model systems to understand the chemical complexity on defect formation and damage accumulation in SP-CSAs under ion irradiation. The high-quality crystals were irradiated at 16 and 300 K to different ion fluences, to form irradiated region with little to heavy damages. Additionally, the ion-induced damage was determined using Rutherford backscattering spectrometry technique along a channeling direction (RBS/C) and the level of lattice damage in irradiated Ni and SP-CSAs was quantified from Monte Carlo (MC) simulations. The results are interpreted using the Multi Step Damage Accumulation model to reveal material damage accumulation kinetics. Key findings of the study are that in case of room temperature irradiations the damage level measured for complex alloys at the highest irradiation fluence of 2 × 10 15 cm -2 (~3 dpa) is significantly higher than that obtained for pure nickel samples and suggest two-step damage accumulation process with a defect transformation taking place at a fluence of about 1.5 × 10 15 cm -2 . Furthermore, structural and damage kinetic differences clearly imply that, with increasing degree of chemical complexity and high solid-solution strengthening effects from Ni to NiFe and to NiFeCoCr, the enhanced lattice stiffness resists to randomization of atomic configurations and inhibits the growth of extended defects.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Interface morphogenesis with a deformable secondary phase in solid-state lithium batteries

Here, the complex morphological evolution of lithium metal at the solid-state electrolyte interface limits performance of solid-state batteries, leading to inhomogeneous reactions and contact loss. Inspired by biological morphogenesis, we developed an interfacial self-regulation concept in which a deformable secondary phase dynamically aggregates at the interface in response to local electro-chemo-mechanical stimuli, enhancing contact. The stripping of a lithium electrode that contains 5 to 20 mole % electrochemically inactive sodium domains causes spontaneous sodium accumulation across the interface, with the sodium deforming to attain intimate electrical contact without blocking lithium transport. This process, characterized with operando x-ray tomography and electron microscopy, mitigates voiding and improves cycling at low stack pressures. The counterintuitive strategy of adding electrochemically inactive alkali metal to improve performance demonstrates the utility of interfacial self-regulation for solid-state batteries.

Yoon, Sun Geun [Georgia Institute of Technology, A↗
DOE OSTI2021

Synthesis, Electronic Structure, and Reactivity of a Planar Four–Coordinate, Cobalt–Imido Complex

A four-coordinate cobalt imido complex, ( tBu mPNP)Co=NMes ( tBu mPNP = modified PNP pincer ligand) has been synthesized from addition of 2,4,6-trimethylphenylazide (Mes–N 3 ) to the corresponding dinitrogen complex. The solid-state structure determined by X-ray diffraction established a rare, idealized planar geometry with a Co=N bond distance of 1.716(2) Å. Magnetic measurements revealed an S = 1 ground state with CAS-SCF calculations supporting radical character on the imide nitrogen. Here, thermolysis of the cobalt-imido compound induced selective insertion of the imido group into a Co–P bond and yielded a three-coordinate cobalt complex with a distorted T-shaped geometry. Transition state analysis conducted with DFT calculations established the thermodynamic stability of the P–N coupled product and provided insight into the exclusive selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Prebiotic Chemistry of Pluto

We present the case for the presence of complex organic molecules, such as amino acids and nucleobases, formed by abiotic processes on the surface and in near-subsurface regions of Pluto. Pluto's surface is tinted with a range of non-ice substances with colors ranging from light yellow to red to dark brown; the colors match those of laboratory organic residues called tholins. Tholins are broadly characterized as complex, macromolecular organic solids consisting of a network of aromatic structures connected by aliphatic bridging units (e.g., Imanaka et al.,2004; Materese et al.,2014, 2015). The synthesis of tholins in planetary atmospheres and in surface ices has been explored in numerous laboratory experiments, and both gas- and solid-phase varieties are found on Pluto. A third variety of tholins, exposed at a site of tectonic surface fracturing called Virgil Fossae, appears to have come from a reservoir in the subsurface. Eruptions of tholin-laden liquid H2O from a subsurface aqueous repository appear to have covered portions of Virgil Fossae and its surroundings with a uniquely colored deposit (D.P. Cruikshank, personal communication) that is geographically correlated with an exposure of H2O ice that includes spectroscopically detected NH3 (C.M. Dalle Ore, personal communication). The subsurface organic material could have been derived from presolar or solar nebula processes, or might have formed in situ. Photolysis and radiolysis of a mixture of ices relevant to Pluto's surface composition (N2, CH4, CO) have produced strongly colored, complex organics with a significant aromatic content having a high degree of nitrogen substitution similar to the aromatic heterocycles pyrimidine and purine (Materese et al.,2014, 2015; Cruikshank et al.,2016). Experiments with pyrimidines and purines frozen in H2O-NH3 ice resulted in the formation of numerous nucleobases, including the biologically relevant guanine, cytosine, adenine, uracil, and thymine (Materese et al.,2017). The red material associated with the H2O ice may contain nucleobases resulting from energetic processing on Pluto's surface or in the interior. Some other Kuiper Belt objects also exhibit red colors similar to those found on Pluto and may therefore carry similar inventories of complex organic materials. The widespread and ubiquitous nature of similarly complex organic materials observed in a variety of astronomical settings drives the need for additional laboratory and modeling efforts to explain the origin and evolution of organic molecules. Pluto observations reveal complex organics on a small body that remains close to its place of origin in the outermost regions of the Solar System.

Cruikshank, D. P.↗
NASA NTRS2011

Modeling Powered Aerodynamics for the Orion Launch Abort Vehicle Aerodynamic Database

Modeling the aerodynamics of the Orion Launch Abort Vehicle (LAV) has presented many technical challenges to the developers of the Orion aerodynamic database. During a launch abort event, the aerodynamic environment around the LAV is very complex as multiple solid rocket plumes interact with each other and the vehicle. It is further complicated by vehicle separation events such as between the LAV and the launch vehicle stack or between the launch abort tower and the crew module. The aerodynamic database for the LAV was developed mainly from wind tunnel tests involving powered jet simulations of the rocket exhaust plumes, supported by computational fluid dynamic simulations. However, limitations in both methods have made it difficult to properly capture the aerodynamics of the LAV in experimental and numerical simulations. These limitations have also influenced decisions regarding the modeling and structure of the aerodynamic database for the LAV and led to compromises and creative solutions. Two database modeling approaches are presented in this paper (incremental aerodynamics and total aerodynamics), with examples showing strengths and weaknesses of each approach. In addition, the unique problems presented to the database developers by the large data space required for modeling a launch abort event illustrate the complexities of working with multi-dimensional data.

Chan, David T.↗
DOE OSTI2025

Triel-Defined Helicity in One-Dimensional III–VI–VII van der Waals Crystals

Inorganic extended lattice solids that bear complex helical motifs manifest unusual physical and quantum states that arise due to their noncentrosymmetric or chiral nature. However, the systematic understanding of how elemental composition influences the structure and physical properties in helical inorganic crystals has been precluded by the rarity of these materials and the lack of modular phases that display such motifs. Here, we report the synthesis of AlSeI single crystals, the first aluminum-containing helical crystal in the III-VI-VII 1D van der Waals class. AlSeI completes the experimentally accessible triel series in the helical selene iodides alongside InSeI and GaSeI. Using the Al, Ga, and In triel series in this selene iodide class, we experimentally demonstrate the evolution of the local quasi-tetrahedral building unit geometry, chain packing, helical parameters, and band gaps based primarily on the identity of the triel atom. Our results underscore the chemical modularity of these phases, the broad range of helical parameters, and the spectrum of electronic states from the visible to the ultraviolet range in this emergent class of 1D, exfoliable, and helical extended lattice solids.

Chemical structure↗
NASA NTRS2004

Computational and Experimental Study of Energetic Materials in a Counterflow Microgravity Environment

Counterflow diffusion flames are studied for various fuels flowing against decomposition products from solid ammonium perchlorate (AP) pellets in order to obtain fundamental understanding of composite propellant flame structure and chemistry. We illustrate this approach through a combined experimental and numerical study of a fuel mixture consisting of C2H4 CO + H2, and C2H2 + C2H4 flowing against solid AP. For these particular AP-fuel systems, the resulting flame zone simulates the various flame structures that are ex+ to exist between reaction products from Ap crystals and a hydrocarbon binder. As in all our experimental studies, quantitative species and temperature profiles have been measured between the fuel exit and AP surface. Species measured included CN, NH, NO, OH, N2, CO2, CO, H2, CO, HCl, and H2O. Temperature was measured using a thermocouple at the exit, spontaneous Raman scattering measurements throughout the flame, OH rotational population distributions, and NO vibrational population distributions. The burning rate of AP was also measured as a function of strain rate, given by the separation distance between the AP surface and the gaseous hydrocarbon fuel tube exit plane. This distance was nominally set at 5 mm, although studies have been performed for variations in separation distance. The measured 12 scalars are compared with predictions from a detailed gas-phase kinetics model consisting of 86 species and 531 reactions. Model predictions are found to be in good agreement with experiment and illustrate the type of kinetic features that may be expected to occur in propellants when AP particle size distributions are varied. Furthermore, the results constitute the continued development of a necessary database and validation of a comprehensive model for studying more complex AP-solid fuel systems in microgravity. Exploratory studies have also been performed with liquid and solid fuels at normal gravity. Because of melting (and hence dripping) and deep thermal wave penetration into the liquid, these experiments were found feasible, but not used for obtaining quantitative data. Microgravity experiments are needed to eliminate the dripping and boiling phenomena of these systems at normal gravity. Microgravity tests in the NASA Glenn 2.2 second drop tower were performed (1) to demonstrate the feasibility of performing propellant experiments using the NASA Glenn microgravity facilities, (2) to develop the operational procedures for safe handing of the energetic materials and disposal of their toxic combustion by-products and (3) to obtain initial measurements of the AP burning rate and flame structure under microgravity conditions. Experiments were conducted on the CH4/AP system previously studied at normal gravity using a modified design of the counterflow burner and a NASA Glenn Pig Rig, i.e., one of the existing drop rigs for general-purpose usage. In these experiments, the AP burning rate was measured directly with a linear variable differential transducer (LVDT) and video imaging of the flame structure was recorded ignition was achieved by hot wires stretched across the AP surfaces. Initial drop tower combustion data show that with the same burner separation distance and flow conditions of the normal gravity experiments, the AP burning rate is approximately a factor of two lower. This difference is likely a result of radiation effects, but further tests with longer test times need to be conducted to verify that steady state conditions were achieved under microgravity conditions.

Takahashi, Fumiaki↗