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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRS2009

Finite-difference simulation and visualization of elastodynamics in time-evolving generalized curvilinear coordinates

Modeling and simulation of free and forced structural vibrations is essential to an overall structural health monitoring capability. In the various embodiments, a first principles finite-difference approach is adopted in modeling a structural subsystem such as a mechanical gear by solving elastodynamic equations in generalized curvilinear coordinates. Such a capability to generate a dynamic structural response is widely applicable in a variety of structural health monitoring systems. This capability (1) will lead to an understanding of the dynamic behavior of a structural system and hence its improved design, (2) will generate a sufficiently large space of normal and damage solutions that can be used by machine learning algorithms to detect anomalous system behavior and achieve a system design optimization and (3) will lead to an optimal sensor placement strategy, based on the identification of local stress maxima all over the domain.

Kaul, Upender K.↗
NASA NTRS2020

Metal-Templated Design of Chemically Switchable Protein Assemblies with High-Affinity Coordination Sites

To mimic a hypothetical pathway for protein evolution, we previously tailored a monomeric protein (cyt cb562) for metal-mediated self-assembly, followed by re-design of the resulting oligomers for enhanced stability and metal-based functions. We show that a single hydrophobic mutation on the cyt cb562 surface drastically alters the outcome of metal-directed oligomerization to yield a new trimeric architecture, (TriCyt1)3. This nascent trimer was redesigned into second and third-generation variants (TriCyt2)3 and (TriCyt3)3 with increased structural stability and preorganization for metal coordination. The three TriCyt variants combined furnish a unique platform to 1) provide tunable coupling between protein quaternary structure and metal coordination, 2) enable the construction of metal/pH-switchable protein oligomerization motifs, and 3) generate a robust metal coordination site that can coordinate all mid-to-late first-row transition-metal ions with high affinity.

Albert Kakkis↗
DOE OSTI2024

Synergistic role of Sn-doping on the thermal and electrical properties of sinnerite Cu 6 As 4 S 9

Sinnerite Cu 6 As 4 S 9 has been identified as a promising material for optoelectronic applications, with potential for other energy-related applications; however, knowledge of the electrical and thermal properties as well as the mechanisms underlying transport in sinnerite is lacking. Here, we present an investigation of the synthesis, structural, thermal and electrical transport properties of stoichiometric and Sn-doped Cu 6 As 4 S 9 . Sinnerite has a triclinic lattice structure, with highly distorted local atomic coordination environments that, in part, results in its complex structure and bonding. Our results and analyses indicate As 4s 2 lone pair-induced distortions and strong lattice anharmonicity that leads to a relatively short phonon mean free path, resulting in intrinsically very low thermal conductivity. The electrical resistivity for both compositions, Cu 6 As 4-x Sn x S 9 (x = 0, 0.2), are relatively high and varies little with temperature, typical of degenerate semiconductors. An increase in mobility and electrical conductivity was obtained by Sn doping in Cu 6 As 3.8 Sn 0.2 S 9 . This work demonstrates an effective route to synthesize bulk sinnerite as well as advances the knowledge of the properties of sinnerite, as this and other ternary chalcogenides continue to be of interest for potential technologically significant applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Synthesis and structural characterization of bis (2-pyridylthio)( p -tolylthio)methyl zinc complexes and the catalytic hydrosilylation of CO 2

Bis(2-pyridylthio)(p-tolylthio)methane, [Bptm STol ]H, has been synthesized by treatment of a 2:1 mixture of 2-mercaptopyridine and p-thiocresol with NaH, followed by addition of CHI3. Access to zinc complexes is provided by the reaction of [Bptm STol ]H with Zn[N(SiMe 3 ) 2 ] 2 to afford [Bptm STol ]ZnN(SiMe 3 ) 2 , from which the halide derivatives [Bptm STol ]ZnX (X = Cl, Br, I) are obtained via reaction with Me 3 SiX (X = Cl, Br, I), and the formate complex, [Bptm STol ]ZnO 2 CH, is obtained by treatment with CO 2 in the presence of PhSiH 3 . Here, the molecular structures of [Bptm STol ]ZnN(SiMe 3 ) 2 , [Bptm STol ]ZnX (X = Cl, Br, I) and [Bptm STol ]ZnO 2 CH have been determined by single crystal X-ray diffraction, which indicate that the four coordinate zinc centers adopt structures that are intermediate between idealized trigonal monopyramidal and seesaw geometries. [Bptm STol ]ZnO 2 CH is a catalyst for the hydrosilylation of CO 2 by (RO) 3 SiH at room temperature to afford the silyl formate, HCO 2 Si(OR) 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Impact of the coordination of multiple Lewis acid functions on the electronic structure and v n configuration of a metal center

Here, the covalent bond classification (CBC) method represents a molecule as ML l X x Z z by evaluating the total number of L, X and Z functions interacting with M. The CBC method is a simplistic approach that is based on the notion that the bonding of a ligating atom (or group of atoms) can be expressed in terms of the number of electrons it contributes to a 2-electron bond. In many cases, the bonding in a molecule of interest can be described in terms of a 2-center 2-electron bonding model and the ML l X x Z z classification can be derived straightforwardly by considering each ligand independently. However, the bonding within a molecule cannot always be described satisfactorily by using a 2-center 2-electron model and, in such situations, the ML l X x Z z classification requires a more detailed consideration than one in which each ligand is treated in an independent manner. The purpose of this article is to provide examples of how the ML l X x Z z classification is obtained in the presence of multicenter bonding interactions. Specific emphasis is given to the treatment of multiple π-acceptor ligands and the impact on the v n configuration, i.e. the number of formally nonbonding electrons on an element of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Method for Real-Time State Estimation of Structural Modes for an Aeroelastic Wind Tunnel Model

A method for estimating displacements, velocities, and accelerations of structural modes in generalized coordinates from measured sensor data in real time is developed and demonstrated. Data from conventional strain gauges and fiber optic strain sensors (FOSS) were combined with strain mode shapes to produce least-squares estimates of the structural mode displacements. Similarly, accelerometer data were combined with displacement mode shapes to estimate structural mode accelerations. Estimates were then combined using a Kalman filter to refine the displacement estimates and produce structural mode velocity estimates. The approach was demonstrated using simulation data for the NASA-Boeing collaboration called the Integrated Adaptive Wing Technology Maturation (IAWTM) project in both a stable open-loop condition and an unstable condition where estimated displacement and velocity states were used for feedback control. Results supported the feasibility of using this approach for feedback control and system identification applications for wind tunnel tests.

Aeroservoelasticity↗
DOE OSTI2023

Systematic study of short- and long-range correlations in RE 3 TaO 7 weberite-type compounds by neutron total scattering and X-ray diffraction

The atomic structures of the lanthanide tantalates, Ln 3 TaO 7 , series (Ln = Pr, Tb, Dy, Ho, Tm, Yb) were systematically investigated using total scattering techniques. High-energy X-ray and neutron diffraction analysis revealed that the long-range structures can be grouped into three distinct families: (1) ordered Cmcm (Ln = Pr), (2) ordered Ccmm (Ln = Tb, Dy, Ho), and (3) disordered, defect-fluorite Fm$\bar{3}$m (Ln = Ho, Tm, Yb). These findings help to clarify the symmetry discrepancy for the already reported long-range structures in the literature. The short-range analysis of neutron total scattering data via pair distribution functions reveals a high degree of structural heterogeneity across length scales for all compounds, with distinct local atomic arrangements that are not fully captured by the average, long-range structure. The short-range structures at the level of coordination polyhedra are better captured by a set of alternative non-centrosymmetric structural models: (1) C2cm, (2) C222 1 , and (3) C2mm. This establishes a short-range multiferroic character for weberite-type tantalates because ferroelectric interactions compete with magnetic correlations. These ferroelectric interactions are particularly pronounced for the disordered compounds Tm 3 TaO 7 and Yb 3 TaO 7 . In conclusion, the structural differences among the three families are the result of changes in TaO 6 polyhedral tilt (transition between families 1 and 2) and dipolar interactions of off-centered Ta cations (transition between families 2 and 3).

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermally stable manganese(Ⅲ) peroxido complexes with hindered N3 tripodal ligands: Structures and their physicochemical properties

Mononuclear manganese(III) peroxido complexes are candidates for the reaction intermediates in manganese containing proteins, such as manganese superoxide dismutase (Mn-SOD) etc. In this study, manganese(III) peroxido complexes [Mn(O 2 )(L3)] and [Mn(O 2 )(L10)] ligated by anionic N3 type ligands with sterically hindered substituents, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (L3 - ) and hydrotris(3-adamantyl-5-isopropyl-1-pyrazolyl)borate (L10 - ), respectively, were structurally characterized. These complexes are the first examples of structurally characterized five-coordinate manganese(III) peroxido complexes. Their characteristic ν(O—O) and ν(Mn—O) stretchings were determined by using H 2 18 O 2 for the first time. Theoretical calculations were performed to obtain further insight into their structural parameters. The decomposed products were obtained as [{Mn III (μ-O)(L3)} 2 Mn IV ] and [Mn III (OH){L10(O)}] from [Mn(O 2 )(L3)] and [Mn(O 2 )(L10)], respectively.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2015

On the Minimum Induced Drag of Wings

Birds do not require the use of vertical tails. They do not appear to have any mechanism by which to control their yaw. As an example the albatross is notable in this regard. The authors believe this is possible because of a unique adaptation by which there exists a triple-optimal solution that provides the maximum aerodynamic efficiency, the minimum structural weight, and it provides for coordination of control in roll and yaw. Until now, this solution has eluded researchers, and remained unknown. Here it is shown that the correct specification of spanload provides for all three solutions at once, maximum aerodynamic efficiency, minimum structural weight, and coordinated control. The implications of this result has far reaching effects on the design of aircraft, as well as dramatic efficiency improvement.

flight mechanics↗
NASA NTRSDate not supplied

Real-Time State Estimation of Structural Modes for an Aeroelastic Wind Tunnel Model

A method is presented for estimating displacements, velocities, and accelerations of structural modes in generalized coordinates from measured sensor data in real time. Specifically, strain data from conventional strain gauges and fiber optic strain sensors (FOSS) were combined with the strain modes (obtained from a finite element model) in a least-squares estimator to produce structural mode displacement estimates and uncertainties. Likewise, accelerometer data were combined with displacement mode shapes in a second least-squares estimator to produce structural mode acceleration estimates. A Kalman filter was then used to refine the displacement estimates and obtain velocity estimates. The method was applied to the half-span wind tunnel test article used in the NASA-Boeing collaboration called the Integrated Adaptive Wing Technology Maturation (IAWTM) project. The technique was found to be useful for real-time control and system identification applications.

Jared A. Grauer↗
DOE OSTI2022

A novel symmetric pyrazine (pyz)-bridged uranyl dimer [UO 2 Cl 3 (H 2 O)(Pyz) 0.5 ] 2 2– : synthesis, structure and computational analysis

In this work, we report on the synthesis of (HPyz + ) 2 [UO 2 Cl 3 (H 2 O)(Pyz) 0.5 ] 2 ·2H 2 O which features a novel pyrazine-bridged uranyl dimer, [UO 2 Cl 3 (H 2 O)(Pyz) 0.5 ] 2 2– . A rigorous computational and experimental analysis of this compound was performed to fully explore the influence of coordination on the electronic structure and potential charge-transfer characteristics of this dimer, revealing a delocalized π-system across the bridging pyrazine and the axial components of both uranyl centers. Electrostatic surface potentials, used to rationalize the observed assembly, indicate a decreased basicity of the uranyl oxo versus [UO 2 Cl 4 ] 2– , and signify a lessened capacity for the terminal –yl oxos of the [UO 2 Cl 3 (H 2 O)(Pyz) 0.5 ] 2 2– dimer to participate in supramolecular assembly. A combined density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM) analysis further evidenced an increase in U═O bond strengths within the dimer, which is supported by a blue shift in the characteristic Raman-active uranyl symmetric stretch (ν 1 ) with respect to the more typically observed [UO 2 Cl 4 ] 2– .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

A comparison of two types of structural optimization procedures for satisfying flutter requirements

A comparison is made of results obtained from mathematical programming and optimality criteria procedures for the minimum-mass design of typical aircraft wing structures to satisfy prescribed flutter requirements. The mathematical programming method is based on an interior penalty function approach. A rigorous optimality criterion and an intuitive optimality criterion based on uniform strain energy density are considered. An intuitive resizing procedure is used for both optimality criterion solutions. All results are calculated using the same computer program, changing only the optimization procedure. Both high- and low-aspect-ratio wings are examined. Finite elements are used for structural modeling, and the generalized coordinates for the flutter solution are based on the natural vibration modes of the structure.

Haftka, R. T.↗
NASA NTRS1991

Macromolecular recognition: Structural aspects of the origin of the genetic system

Theoretical simulation of prebiotic chemical processes is an invaluable tool for probing the phenomenon of the evolution of life. Using computational and modeling techniques and guided by analogies from present day systems, we seek to understand the emergence of the genetic apparatus, enzymatic catalysis and protein synthesis under prebiotic conditions. Modeling of the ancestral aminoacyl-tRNA-synthetases (aRS) may provide important clues to the emergence of the genetic code and the protein synthetic machinery. The minimal structural requirements for the catalysis of tRNA aminoacylation are being explored. A formation of an aminoacyl adenylate was studied in the framework of ab initio molecular orbital theory. The role of individual residues in the vicinity of the TyrRS active site was examined, and the effect of all possible amino acids substitutions near the active site was examined. A formation of aminoacyl tRNA was studied by the molecular modeling system SYBYL with the high resolution crystallographic structures of the present day tRNA, aRS's complexes. The ultimate goal is to propose a simple RNA segment that is small enough to be build in the primordial chemical environment but maintains the specificity and catalytic activity of the contemporary RNA enzyme. To understand the mechanism of ribozyme catalyzed reactions, ab initio and semi-empirical (ZINDO) programs were used to investigate the reaction path of transphosphorylation. A special emphasis was placed on the possible catalytic and structural roles played by the coordinated magnesium cation. Both the inline and adjacent mechanisms of transphosphorylation were studied. The structural characteristics of the target helices, particularly a possible role for the G-T pair, is also studied by a molecular dynamics (MD) simulation technique.

Rein, Robert↗
DOE OSTI2022

PGM-Free Oxygen-Reduction Catalyst Development for Proton-Exchange Membrane Fuel Cells: Challenges, Solutions, and Promises

Proton-exchange membrane fuel cells (PEMFCs) are efficient and clean hydrogen energy technologies for transportation and stationary applications. Highly active and durable low-cost cathode catalysts for the oxygen-reduction reaction (ORR) under challenging acidic environments are desperately needed to address the cost and durability issues of PEMFCs. The most promising platinum group metal (PGM)-free catalysts for the ORR in acidic media are atomically dispersed and nitrogen-coordinated metal site catalysts denoted as M–N–C, M = Fe, Co, or Mn. Due to significant efforts in the past few decades, these catalysts have demonstrated much-improved ORR activity and promising initial fuel cell performance approaching traditional Pt/C catalysts. However, the insufficient long-term stability (up to 5000 h) under PEMFC operation represents a primary technical barrier to making current PGM-free catalysts less viable yet in PEMFCs. In this Account, we highlight recent advances in synthesizing efficient PGM-free catalysts for the ORR in PEMFCs, emphasizing effective strategies to improve mass and intrinsic activity and the possible degradation mechanisms. In particular, a chemical doping method based on the zeolitic imidazolate framework (ZIF)-8 represents the key to developing efficient M–N–C catalysts containing atomically dispersed and nitrogen-coordinated single metal active sites (i.e., MN 4 ). The newly acquired understanding of the formation mechanism of MN 4 active sites during the thermal activation and its correlation to catalytic properties guide the rational catalyst design rather than relying on current trial-and-error approaches. Considerable efforts have further been invested in increasing the active site density and enhancing intrinsic activity by regulating carbon-phase structures and the local coordination environment. Furthermore, these highly active catalysts usually suffer from significant activity loss during the ORR. Therefore, breaking the activity–stability trade-off is the key to simultaneously achieving activity and stability in one catalyst, which is discussed on the basis of our recent successes in regulating local carbon structures surrounding active single metal sites. Significant research efforts toward understanding the degradation mechanisms and improving the lifetime of PGM-free catalysts are still crucial for viable applications in the future. Novel electrode designing strategies are needed to translate the PGM-free catalysts’ ORR activity to solid-state electrolyte-based membrane electrode assemblies (MEAs) with robust three-phase (i.e., gas–liquid–solid) interfaces for efficient charge and mass transports for performance improvement. On the basis of our effort at the University at Buffalo supported by ElectroCat Consortium associated with U.S. DOE’s Hydrogen and Fuel Cell Technologies Office, we provide a perspective on PGM-free cathode catalysts concerning remaining bottlenecks and future opportunities, aiming to inspire the community in both mechanistic understanding and technological development.

08 HYDROGEN↗
DOE OSTI2025

Alkaline Earth-Based Ternary Chalcogenide Nanocrystals: Cadmium- and Lead-Free Optical Materials

As some of the most abundant elements on the Earth’s crust, alkaline earths bear great potential in Cd- and Pb-free catalytic, energy conversion, and light-emitting devices. Further, because large electropositive alkaline earths (Ae) can adopt high coordination numbers, they offer structural complexity beyond the tetrahedral (c-Si, II–VI, III–V) or octahedral (IV–VI) atomic sites that─with the notable exception of halide perovskites─are ubiquitous among nanocrystalline semiconductors. Here, in this work, we present a general route to photoluminescent 6–125 nm nanocrystals of ternary AeIn 2 Ch 4 semiconductors (Ae = Sr, Ba; Ch = S, Se) featuring eight- (Ae) as well as four-coordinate (In and Ch) atomic sites. Powder X-ray diffraction, electron microscopy, optical absorption, photoluminescence, and solid-state (ss)NMR spectroscopies attest to the ternary composition and phase purity of the nanocrystals. Continuous shape measures pinpoint the degree of distortion of individual crystallographic sites from ideal coordination polyhedra, allowing us to identify two very distinct types of Se coordination environments. Based on their higher order, pseudo-3-fold rotational symmetry, we assign 77 Se ssNMR peaks with negligible chemical shift anisotropy (CSA) to pyramidalized Se sites with vacant-trigonal bipyramid-like geometries and those with larger CSA to lower symmetry Se sites with seesaw-distorted geometries. Calculations help to better understand the electronic band structure of these materials. The nanocrystals are stable at room temperature in open air for several weeks, and some compositions up to 1000 °C under Ar, making them strong candidates for practical applications.

alkaline earth↗
NASA NTRS1993

Damage detection using experimentally measured mass and stiffness matrices

A method is presented for locating physical damage or change in a structure using experimentally measured mass and stiffness matrices. The approach uses a recently developed algorithm for transforming a state-space realization into a second order structural model with physical displacements as the generalized coordinates. This is accomplished by first rotating a state-space model of the identified structural dynamics into modal coordinates and approximating the mass normalized modal vectors for the output measurement set. Next, the physical mass, damping and stiffness matrices are synthesized directly from the measured modal parameters. This yields experimental mass and stiffness matrices for the structure without the use of a finite element model or a numerical search. The computed mass and stiffness are asymptotically equivalent to a static condensation of the global physical coordinate model. Techniques for solving the inverse connectivity problem are then developed whereby it is possible to assess the stiffness in a region of the structure bounded by several sensors. Applications to both simulated data and experimental data are used to discuss the effectiveness of the approach.

Peterson, L. D.↗
DOE OSTI2022

Hybrid manufacturing of Invar mold for carbon fiber layup using structured light scanning

This paper describes coordinate system definition and transfer for five-axis machining of additively-manufactured preforms. In this method, a set of fiducials are attached to the temporarily attached to the part, and their location relative to the preform geometry is calibrated using a structured light scanner. Those fiducials can then be measured in the machine tool to determine the location and orientation of the part. The method is demonstrated by finish-machining a carbon fiber layup mold from an additively manufactured Invar preform. In addition to showing the coordinate transfer methods necessary to machine the part, several key challenges with machining additively-manufactured preforms are discussed and potential solutions are proposed. Unfortunately, the final part was ultimately unusable due to porosity inside the part left from the additive process. Future work will remanufacture this part while taking steps to avoid porosity and other challenges encountered.

36 MATERIALS SCIENCE↗