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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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An apparatus for solid state energy harvesting includes a complex oxide based pyrochlores having a chemical formula of A2 B2 O7 configured to directly convert heat into electricity and operate and function at a higher temperature without oxidizing in air. The complex oxide based pyrochlores are mixed with cation at B-site.
Direct study of changes in catalyst structure-kinetic properties during redox transitions using a new time-resolved technique The Temporal Analysis of Products (TAP) pulse response methodology1 is a transient technique offering the time scale needed to deconvolve many reaction steps from the complex network typical to industrial catalytic processes. The traditional TAP measurement observes the gas phase dynamic response but, hereto now, has been devoid of any direct measurement of change in the catalyst itself. The development of an operando technique that couples gas phase transient kinetics to dynamic metal centers and surface species is presented. Significance Unification of the TAP methodology with time-resolved spectroscopic measurement can offer unprecedented insight into the complex kinetic phenomena regulated by the solid catalyst.
The Sample Analysis at Mars (SAM) instrument onboard Curiosity can perform pyrolysis of martian solid samples, and analyze the volatiles by direct mass spectrometry in evolved gas analysis (EGA) mode, or separate the components in the GCMS mode (coupling the gas chromatograph and the mass spectrometer instruments). In addition, SAM has a wet chemistry laboratory designed for the extraction and identification of complex and refractory organic molecules in the solid samples. The chemical derivatization agent used, N-methyl-N-tert-butyldimethylsilyl- trifluoroacetamide (MTBSTFA), was sealed inside seven Inconel metal cups present in SAM. Although none of these foil-capped derivatization cups have been punctured on Mars for a full wet chemistry experiment, an MTBSTFA leak was detected and the resultant MTBSTFA vapor inside the instrument has been used for a multi-sol MTBSTFA derivatization (MD) procedure instead of direct exposure to MTBSTFA liquid by dropping a solid sample directly into a punctured wet chemistry cup. Pyr-EGA, Pyr-GCMS and Der-GCMS experiments each led to the detection and identification of a variety of organic molecules in diverse formations of Gale Crater.
Growth in power requirements and the complexity of emerging distribution systems are creating the need for new solid-state products for many applications. The qualification requirements, testing standards and life-cycle management practices of solid-state devices used in protection applications is not established. The project will leverage newly developed accelerated testing capabilities design specifically for protection applications to generate large data sets that will enable advanced digital techniques for data analysis and embedded health monitoring.
There is a strategic interest in understanding how the propellant manufacturing process contributes to military capabilities outside the United States. The paper will discuss how system dynamics (SD) has been applied to rapidly assess the capabilities and vulnerabilities of a specific composite propellant production complex. These facilities produce a commonly used solid propellant with military applications. The authors will explain how an SD model can be configured to match a specific production facility followed by a series of scenarios designed to analyze operational vulnerabilities. By using the simulation model to rapidly analyze operational risks, the analyst gains a better understanding of production complexities. There are several benefits of developing SD models to simulate chemical production. SD is an effective tool for characterizing complex problems, especially the production process where the cascading effect of outages quickly taxes common understanding. By programming expert knowledge into an SD application, these tools are transformed into a knowledge management resource that facilitates rapid learning without requiring years of experience in production operations. It also permits the analyst to rapidly respond to crisis situations and other time-sensitive missions. Most importantly, the quantitative understanding gained from applying the SD model lends itself to strategic analysis and planning.
Abstract Indium and bismuth are technologically important elements, in particular as oxides for optoelectronic applications. 115 In and 209 Bi are both I = 9/2 nuclei with high natural abundances and moderately high frequencies but large nuclear electric quadrupole moments. Leveraging the quadrupolar interaction as a measure of local symmetry and polyhedral distortions for these nuclei could provide powerful insights on a range of applied materials. However, the absence of reported nuclear magnetic resonance (NMR) parameters on these nuclei, particularly in oxides, hinders their use by the broader materials community. In this contribution, solid‐state 115 In and 209 Bi NMR of three recently discovered quaternary bismuth or indium oxides are reported, supported by density functional theory calculations, numerical simulations, diffraction and additional multinuclear ( 27 Al, 69,71 Ga, and 121 Sb) solid‐state NMR measurements. The compounds LiIn 2 SbO 6 , BiAlTeO 6 , and BiGaTeO 6 are measured without special equipment at 9.4 T, demonstrating that wideline techniques such as the QCPMG pulse sequence and frequency‐stepped acquisition can enable straightforward extraction of quadrupolar tensor information in I = 9/2 115 In and 209 Bi even in sites with large quadrupolar coupling constants. Relationships are described between the NMR observables and local site symmetry. These are amongst the first reports of the NMR parameters of 115 In, 121 Sb, and 209 Bi in oxides.
For presentation at the AIChE Annual Meeting, Orlando, FL, November 5-10, 2023.
Single-crystal microstructure can bring high performance for many materials includingpiezoelectrics1, 2, semiconductors3, 4, and cuprate superconductors5. Unlike single-crystal metalsthat can be machined into complex components6, most single-crystal ceramics are limited to theshape of thin films or plates due to their brittleness. However, more designs of advanced devicesneed to break these geometric limitations. 3D-ink-printing can efficiently fabricate complex architectured ceramics, but the microstructure is polycrystals. Here, for the first time, we demonstrate a route to grow single-crystal on 3D printed ceramic-YBa2Cu3O7-x (YBCO)superconductors that can simultaneously have complex architectures and high critical currentdensity. An ink containing precursor powders was 3D extruded and sintered to obtain polycrystalYBCO micro-lattices. A single-crystal seed is then utilized to grow single crystal on 3D-printedmicro-lattices by melt growth method. We found that the geometric details of 3D printed microlatticecan survive after it went through liquid + solid phase region above its peritectic temperature.More complex YBCO single-crystal parts, such as horizontal and toroidal coils, were thensuccessfully fabricated. In addition, Origami can be implemented on our 3D printed sample to increase their complexity. This research provides a new way to develop superconducting devicessuch as undulators for synchrotron radiation and microwave cavities for dark-matter axion search7.We expect this new process will inspire more studies about 3D printing of single-crystal ceramics. For example, 3D printing of BaTiO3 can be developed to grow a single crystal8 for the applications of dielectric capacitors and transducers.
Enhanced polarization of target nuclei can be measured via the complex impedance of a resonant circuit coupled to the target while sweeping the circuit through the nuclear Larmor frequency, observing the absorption or emission of energy by the spins in the material. For decades, solid polarized targets at Jefferson Lab have relied upon continuous-wave Nuclear Magnetic Resonance polarization measurements using Liverpool Q-meter systems. These Liverpool Q-meters are no longer produced, and replacing the aging components is becoming increasingly difficult. The polarized target group at Bochum has produced replacement Q-meters in the Liverpool style using modern components, and we are following their example while researching improvemnts to the technique. We discuss our efforts to produce improved Q-meters for upcoming experiments utilizing solid polarized targets in Jefferson Lab's Hall B.
Abstract Vibrational spectroscopy allows us to understand complex physical and chemical interactions of molecular crystals and liquids such as ammonia, which has recently emerged as a strong hydrogen fuel candidate to support a sustainable society. We report inelastic neutron scattering measurement of vibrational properties of ammonia along the solid-to-liquid phase transition with high enough resolution for direct comparisons to ab-initio simulations. Theoretical analysis reveals the essential role of nuclear quantum effects (NQEs) for correctly describing the intermolecular spectrum as well as high energy intramolecular N-H stretching modes. This is achieved by training neural network models using ab-initio path-integral molecular dynamics (PIMD) simulations, thereby encompassing large spatiotemporal trajectories required to resolve low energy dynamics while retaining NQEs. Our results not only establish the role of NQEs in ammonia but also provide general computational frameworks to study complex molecular systems with NQEs.
Abstract The DART (Double Asteroid Redirection Test) mission will impact a spacecraft on the secondary (Dimorphos) of the binary asteroid system Didymos in 2022 September, with the goal of altering the orbital period of Dimorphos about Didymos sufficiently to be observed from ground-based observations. Numerical impact modeling is a crucial component in understanding the outcome of the DART experiment, and while many have investigated the effects of target properties, such as material strength and porosity (which remain unknown), an often overlooked factor is the importance of accurately representing the spacecraft itself in such models. Most impact modeling to date has considered simple impactor geometries such as a solid uniform sphere, but in reality the spacecraft is a complex shape full of different components, open spaces, and thin walled structures. At a minimum, a simple solid representation underestimates the surface area of the impact: for a small body such as Dimorphos (approximately 160 m in diameter), the difference between a spacecraft spanning 20 m (including solar arrays) impacting and a sub-1 m idealized shape may be important. In this paper, we compare models impacting high-fidelity models of the spacecraft based on the CAD geometry with various simplified impactors, in order to assess the potential importance of this effect. We find that the difference between the simplest impactor geometries (such as a uniform sphere) and the real spacecraft is measurable, and has an interesting dependence on the material properties of the asteroid itself.
Throughout U.S. Department of Energy (DOE) complexes, safety engineers employ the five-factor formula to calculate the source term (ST) that includes parameters of airborne release fraction (ARF), respirable fraction (RF) and damage ratio (DR). Limited experimental data on fragmentation of solids, such as ceramic pellets (i.e., PuO2), and container breach due to mechanical insults (i.e., drop and forklift impact), can be supplemented by modeling and simulation using high fidelity computational tools to estimate these parameters. This paper presents the use of Sandia National Laboratories' SIERRA solid mechanics (SM) finite element code to investigate the behavior of the widely utilized waste container (such as 7A Drum) subject to a range of free fall impact and puncture scenarios. The resulting behavior of the container is assessed, and the estimates are presented for bounding DRs from calculated breach areas for the various accident conditions considered. This paper also describes a novel multiscale constitutive model recently implemented in SIERRA/SM that simulates the fracture of brittle materials such as PuO 2 and determines ARF during the fracture process. Furthermore, comparisons are made between model predictions and simple bench-top experiments.
A fundamental understanding of radium (Ra) coordination chemistry has been hindered by the scarcity and radiological hazards of 226 Ra, leaving the structural characterization of molecular Ra complexes almost entirely unexplored. Here, we introduce a polyoxometalate (POM)-assisted crystallization strategy that enables single-crystal X-ray diffraction analysis of Ra–chelator complexes from microgram-scale samples. Employing the plenary Keggin anion [SiW 12 O 40 ] 4– , we isolated and structurally characterized Ra 2+ complexes of 18-crown-6 and the bis-picolinate macrocycle macropa, together with their Sr 2+ and Ba 2+ analogues. The resulting structures reveal systematic, size-dependent trends in coordination number and metal-donor distances across the alkaline earth series and provide the first direct experimental measurements of Ra–N and Ra–OCOO bond distances. Together, these results establish POM-assisted crystallization as a robust approach for obtaining solid-state structural information on Ra 2+ complexes of organic chelators, opening new opportunities to advance the coordination chemistry needed to fully realize radium’s potential in isotope production and targeted radiotherapy. More broadly, this approach expands the experimental toolkit available for studying scarce, highly radioactive elements accessible only in microgram quantities.
Abstract A hybrid Monte-Carlo molecular-dynamics method for determining solidus and liquidus compositions in multicomponent systems is presented that overcomes both the time limitations in conventional molecular dynamics that prevent the evolution of distinct solid and liquid compositions via diffusion and the complexity challenge that prevents use of thermodynamic assessment in systems of many components. This hybrid method is validated in the Cu–Ni system against an independent assessment of solidus and liquidus compositions based on the regular solution model. Strategies for efficient mapping of different phase diagrams, based on the thermodynamic parameter T 0 , the temperature at which two phases of the composition X 0 have equal free energies, are presented and then demonstrated for the copper-nickel fully miscible system and the gold–silicon eutectic system. A calculation of the solidus and liquidus sampled during the equilibrium melting of equiatomic CrMnFeCoNi is performed, indicating that this method has potential to be extended to the study of many component alloys.
Here, this study explores the transport of rare earth elements (REE) in acidic sulfate-bearing hydrothermal fluids and the implications for the fractionation of light/heavy REE in critical mineral deposits. The speciation of Nd (light REE) and Yb (heavy REE) sulfate complexes were determined via in situ Raman spectroscopy using fused SiO 2 capillary cells up to 300 ºC at saturated water vapor pressure and in a hydrothermal diamond anvil cell up to 500 ºC and 540 MPa. The REE monosulfate (REESO 4 + ) and REE disulfate (REE(SO 4 ) 2 - ) species are stable below 150 to 250 ºC but become less stable at higher temperatures, particularly the light REE, due to the decreased solubility of REE sulfate solids. At higher pressure, these REE sulfate complexes display an increased stability field up to 400 ℃. The REE bisulfate complex (REEHSO 4 2+ ) was identified with a wide stability field below 400 ºC for the HREE in acidic Yb 2 (SO 4 ) 3 -bearing solutions, whereas in Nd 2 (SO 4 ) 3 -bearing solutions, the LREE bisulfate complex is restricted to below 100 ℃. These results suggest that bisulfate is a previously unrecognized selective ligand for heavy REE transport at low temperature in acidic oxidized hydrothermal fluids. Such fluids are responsible for hydrothermal alteration in many REE deposits. Prediction of phase stabilities across pressure, temperature, and composition space (P-T- x ) is crucial for predicting the role of aqueous REE sulfate complexes in the mobilization of REE in crustal fluids.
The preparation and control of quantum states lie at the heart of quantum information science. Recent advances in solid-state quantum emitters (QEs) and nanophotonics have transformed the landscape of quantum photonic technologies, enabling scalable generation of quantum states of light and matter. A new frontier in solid-state quantum photonics is the engineering of many-body interactions between QEs and photons to achieve robust coherence and controllable many-body entanglement. These entangled states, including photonic graph and cluster states, superradiant emission and emergent quantum phases, are promising for quantum computation, sensing and simulation. However, intrinsic inhomogeneities and decoherence in solid-state platforms pose considerable challenges in realizing such complex entangled states. This Review provides an overview of fundamental many-body interactions and dynamics at the light–matter interfaces of solid-state QEs and discusses recent advances in mitigating decoherence and harnessing robust many-body coherence.
The group IIF iron meteorites and Eagle Station pallasites (PES) have highly siderophile element abundances (HSE; Re, Os, Ir, Ru, Pt, and Pd) of metal that are consistent with formation in planetesimal cores by fractional crystallization with minor to major solid metal-liquid metal mixing. Modeling of HSE abundances of the IIF irons indicates a complex formation history that included the mixing of primitive and evolved solid and liquid metals. By contrast, modeling of HSE abundances of PES metal suggests these meteorites formed mainly as equilibrium solids from a common liquid. Abundances of some of the siderophile elements in the IIF irons and PES are permissive of a common core origin, however, the abundances of W and Ni indicate the PES ultimately formed on a more oxidized body. The PES most likely formed by the injection of olivine present at the core-mantle boundary into a metallic core liquid as a result of impact. The core then crystallized inward, trapping the olivine.