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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Isolation of Inner-Sphere Aquo Complexes of Samarium(II)

The cis-anti-cis and cis-syn-cis isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 exhibiting trans water molecules bound to the Sm 2+ ion have been isolated and characterized. Sm 2+ possesses an electrochemical potential sufficient for water reduction, and thus these complexes add to the recent body of evidence that the oxidation of Sm 2+ by water can operate by a mechanism that is not straightforward. These complexes are obtained by the direct addition of stoichiometric amounts of water to solutions of the respective Sm(dicyclohexano-18-crown-6)I 2 isomers under an inert atmosphere. The parent complex, Sm(dicyclohexano-18-crown-6)I 2 , lacking coordinating water molecules can be obtained through rigorous exclusion of water. It was determined that the bulky cyclohexano-substituents deter intramolecular interactions between [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 complexes and slow the oxidization of the metal centers. The extent of the stability of these complexes to the presence of water has been further probed through cyclic voltammetry, where it was found that the redox potential of both isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 maintains quasi-reversible behavior with a 50,000-fold excess of water to Sm 2+ in solution with the cis-syn-cis complex being quasi-reversible at even higher concentrations of water. Solution-phase spectroscopy of these complexes in acetonitrile shows a corresponding hypsochromic shift of the Sm 2+ 4f → 5d transition typically observed in the visible region from Sm 2+ complexes. Here, the crystalline compounds obtained in this study support solid-state spectroscopic trends observed from other Sm 2+ crown-ether complexes containing iodide counterions, wherein the proximity of the iodide ions to the metal center determines whether the complex can exhibit 4f → 4f photoluminescence.

Crystals↗
DOE OSTI2021

Quantifying the chemical, electrochemical heterogeneity and spatial distribution of (poly) sulfide species using Operando SANS

In-situ and operando measurements are done to gain a better understanding of the precipitation mechanisms during charge and discharge in lithium sulfur batteries. A carbon felt networked with microfibers consisting of pores, 2 nm and smaller, is used as a freestanding sulfur host. Three different methods of sulfur infiltration are explored in order to determine the best one to fill most of the pores. It was identified to be a melt infiltration method in a vacuum oven, where the pores including the ultra-micropores, are successfully filled. In-situ electrochemical impedance spectroscopy measurements show a solid product formation occurring at the sulfur cathode, both during the high voltage plateau and at the end of discharge. In a 3-electrode EIS measurement, a similar solid product formation on the Li counter electrode due to its reaction with polysulfides is also observed. Operando small angle neutron scattering measurements show the solid product formation, in the carbon, both near the beginning and at the end of discharge, confirming the precipitation data via contrast changes as a function of charge and discharge. It is shown that Li 2 S precipitates in the pores at the beginning and the end of discharge, whereas S8 precipitates on the surface of the carbon felt. Finally, this lithium sulfur system shows both the quasi-solid-state and the solid-liquid-solid reactions in a typical ethereal electrolyte solution with a two-plateau discharge profile.

25 ENERGY STORAGE↗
DOE OSTI2023

A sharp interface Lagrangian-Eulerian method for flexible-body fluid-structure interaction

This paper introduces a sharp-interface approach to simulating fluid-structure interaction (FSI) involving flexible bodies described by general nonlinear material models and across a broad range of mass density ratios. This new flexible-body immersed Lagrangian-Eulerian (ILE) scheme extends our prior work on integrating partitioned and immersed approaches to rigid-body FSI. Our numerical approach incorporates the geometrical and domain solution flexibility of the immersed boundary (IB) method with an accuracy comparable to body-fitted approaches that sharply resolve flows and stresses up to the fluid-structure interface. Unlike many IB methods, our ILE formulation uses distinct momentum equations for the fluid and solid subregions with a Dirichlet-Neumann coupling strategy that connects fluid and solid subproblems through simple interface conditions. As in earlier work, we use approximate Lagrange multiplier forces to treat the kinematic interface conditions along the fluid-structure interface. This penalty approach simplifies the linear solvers needed by our formulation by introducing two representations of the fluid-structure interface, one that moves with the fluid and another that moves with the structure, that are connected by stiff springs. This approach also enables the use of multi-rate time stepping, which allows us to use different time step sizes for the fluid and structure subproblems. Our fluid solver relies on an immersed interface method (IIM) for discrete surfaces to impose stress jump conditions along complex interfaces while enabling the use of fast structured-grid solvers for the incompressible Navier-Stokes equations. The dynamics of the volumetric structural mesh are determined using a standard finite element approach to large-deformation nonlinear elasticity via a nearly incompressible solid mechanics formulation. This formulation also readily accommodates compressible structures with a constant total volume, and it can handle fully compressible solid structures for cases in which at least part of the solid boundary does not contact the incompressible fluid. Selected grid convergence studies demonstrate second-order convergence in volume conservation and in the pointwise discrepancies between corresponding positions of the two interface representations as well as between first and second-order convergence in the structural displacements. The time stepping scheme is also demonstrated to yield second-order convergence. To assess and validate the robustness and accuracy of the new algorithm, comparisons are made with computational and experimental FSI benchmarks. Test cases include both smooth and sharp geometries in various flow conditions. Furthermore, we also demonstrate the capabilities of this methodology by applying it to model the transport and capture of a geometrically realistic, deformable blood clot in an inferior vena cava filter.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Optimization of the compositions of polyanionic sodium-ion battery cathode NaFe 2-x V x (PO 4 )(SO 4 ) 2

Sodium (Na) super ionic conductor (NASICON) polyanionic compounds have recently attracted much attention from the battery community because of their electroactive properties and reasonably high ionic conductivities, leading to their use as a cathode in sodium-ion batteries. This article describes the compositional optimizations, crystallographic evaluations, and electrochemical behavior of a new mixed NASICON polyanionic compound, NaFe 2-x V x (PO 4 )(SO 4 ) 2 . By doping the characteristic Fe 3+ sites of the FeO 6 octahedrons with varying amounts of V 3+ , the electrochemical stability and charge transport in NaFe 2 (PO 4 )(SO 4 ) 2 were enhanced. The resulting best composition, with crystal structure NaFe 1.4 V 0.6 (PO 4 )(SO 4 ) 2 resolved through the Rietveld method, exhibited a stable capacity compared with the other synthesized compositions. In situ powder x-ray diffraction measurements, a single-phase intercalation/deintercalation mechanism of the NASICON structure in the measured sodium concentration window was observed with no impurity phase formation. Further electrochemical assessments revealed the interfacial charge transfer kinetics to be the rate-limiting step in the sodium concentration window. Also, the measured sodium-ion diffusivity values in the range of 6 × 10 -11 to 7 × 10 -11 cm 2 /s in the measured sodium concentration range. The results reported here highlight the potential of compositionally and morphologically optimized NaFe 1.4 V 0.6 (PO 4 )(SO 4 ) 2 with higher particle surface areas as a cathode material for high-performance sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Tuning the Radius Ratio to Enhance Thermoelectric Properties in the Zintl Compounds AM 2 Sb 2 (A = Ba, Sr; M = Zn, Cd)

Five novel Zintl phase solid solutions in the Ba 1–x Sr x Zn 2–y Cd y Sb 2 (0 ≤ x ≤ 0.13(1); 0 ≤ y ≤ 0.32(2)) system were successfully synthesized by the molten Pb metal-flux method, and the powder X-ray diffraction and single-crystal X-ray diffraction analyses proved that all five title compounds adopted the BaCu 2 S 2 -type phase having the orthorhombic Pnma space group (Z = 4, Pearson code oP20) with five crystallographically independent atomic sites. The previously studied BaCu 2 S 2 -type antimonides demonstrated a limited tolerance for doping in contrast to the CaAl 2 Si 2 -type antimonides. To understand the relatively narrower phase width and limited dopability of the title BaCu 2 S 2 -type phase than the CaAl 2 Si 2 -type phase in the overall Ba 1–x Sr x Zn 2–y Cd y Sb 2 system, the radius ratio of cations and anionic elements r + /r – for two structure types were thoroughly investigated. For the first time, the r + /r – ratio was identified as a critical factor for the phase selectivity: (1) r + /r – > 1 favored the BaCu 2 S 2 -type phase, and (2) r + /r – < 1 favored the CaAl 2 Si 2 -type phase. Further, we also revealed the structural transformation mechanism from the more widely observed CaAl 2 Si 2 -type phase to the title BaCu 2 S 2 -type phase as the relatively larger cationic elements were introduced to the system. A series of DFT calculations using the three hypothetical models indicated that a resonance peak near EF in the density of states curves was descended from the relatively flat band structure at several special symmetry points rationalizing the enhanced Seebeck coefficients of Ba 0.94(1) Sr 0.06 Zn 1.86(3) Cd 0.14 Sb 2 and Ba 0.96(1) Sr 0.04 Zn 1.68(2) Cd 0.32 Sb 2 . Electron localization function analysis rationalized the correlation between the polarity change of anionic Zn/Cd–Sb bonds and the charge carrier mobility on the anionic frameworks. Temperature-dependent thermoelectric properties were studied for the four title compounds, and the results proved that the Sr and Cd doping in the title Ba 1–x Sr x Zn 2–y Cd y Sb 2 system successfully enhanced the ZT values through the increased Seebeck coefficients and the reduced total thermal conductivities.

36 MATERIALS SCIENCE↗
NASA NTRS2016

Hybrid Propulsion In-Situ Resource Utilization Test Facility Results for Performance Characterization

Hybrid propulsion presents a promising alternative to conventional systems for in-space propulsion applications using In-Situ Propellant Production (ISPP). A hybrid propulsion test facility has been built at the NASA Jet Propulsion Laboratory (JPL) with the capability of evaluating ISPP oxidizers (gaseous mixtures of O2 and CO2) and modifying fuel type and chamber geometry. This work is the result of a continuing e ort at JPL to characterize the burn characteristics and performance of different propellant combinations and motor configurations in order to re ne and support preliminary designs. Twelve tests using gaseous oxygen and two paraffin based fuels (Black Paraffin and SP1X) from the 2015 campaign are presented. Different reduction techniques are compared in an e ort to determine the uncertainty associated with deriving a regression rate law and evaluating c* efficiency with the collected data.Hybrid motors are mechanically and chemically simple propulsion systems that have the potential forlong-term storability with low gross mass. The oxidizer (such as gaseous O2) can be produced in-situ,signicantly reducing the landed mass. The solid, inert fuel is stored in the combustion chamber in its most dense state, further reducing the total structural mass and volume. Considerable eorts have been focusedon ISPP for Environmental Control and Life Support Systems (ECLSS) and human exploration of Mars.At optimum oxidizer to fuel ratio (O/F), about 70% of the total propellant mass could be produced in-situ.Paran based fuels exhibit a fast regression rate behavior due to the formation of a thin liquid layer on thefuel surface.1 A high burn rate is necessary in order to reach a medium to high thrust range. In order toachieve an O/F ratio close to optimum performance (between 2.1 and 2.7 for the O2/Paran combination),the fuel mass ow needs to be suciently large compared to the oxidizer ow. The slow regression rateof classical hybrid rocket fuels leads to long fuel grain designs or complicated multi-port structures. Singleport, high regression rate fuels have the potential to reduce residual propellant mass and have a grainlength to diameter ratio (L/D) more favorable for packaging. However, hybrid motors remain at a fairly lowTechnology Readiness Level (TRL), and solutions to accurately measure and increase performance are stilllacking, especially for small-scale motors that are constrained to tight packaging.A total of 12 hotres were performed and analyzed in this campaign. All of these tests were conductedat pressures above the critical pressure of paran wax, approximately 6.7 bar (97 psi).2 Three dierentmotor congurations were explored while conserving a single cylindrical port fuel grain. Additionally, sincethrottling is a crucial advantage of hybrid rocket propulsion systems, low oxidizer mass ows (60 - 100 g/s)and uxes (5 - 30 g/cm2/s) were investigated to determine the performance impact in this regime.

Mechentel, F. S.↗
DOE OSTI2022

Mass transport in a highly immiscible alloy on extended shear deformation

Forced mixing to a single phase or supersaturated solid solution (SSS) and its prerequisite microstructure evolution in immiscible systems has been a focus of research for both fundamental science and a variety of applications. Controlling the formation of SSS by shear deformation assisted processing could enable a material design beyond conventional equilibrium microstructure in immiscible systems. Here, a highly immiscible (mixing enthalpy of ~ 20 kJ·mol -1 ) Cu-50 at. % Cr binary alloy was employed to investigate the microstructure evolution and localized tendencies of SSS during severe shear deformation. The present results demonstrate distinctive microstructure refinement process in each phase and how they lead to localized SSS as a function of shear strain. Preferential dynamic recrystallization occurs in the softer Cu phase due to strain localization, leading to substantial grain refinement. The refinement of Cr phase in the top-most layer, however, is enabled by the progressive evolution of grain lamination, splitting, and fragmentation as a function of shear strain. The eventual SSS is found to be strongly dependent on the local environments that affect the dislocation activity, including the level of microstructure refinement, the interfacial orientation relationship, hardness difference, and supposed stability of oxidation. Ab initio simulations comfirm that it is more favorable to oxidize Cr than Cu at incoherent Cu/Cr interfaces which then limits the mass transport on an incoherent boundary. Our results shed light on the underpinning mechanism for non-equilibrium mass transport in immiscible systems upon severe deformation that can be applicable to a variety of processing techniques aimed at producing immiscible alloys with superior mechanical properties.

36 MATERIALS SCIENCE↗
NASA NTRS2000

Particle Engulfment and Pushing Micro-Gravity Experiments and Mathematical Modeling

The phenomenon of interaction of particles with solid-liquid interfaces that results in particle engulfment or pushing (PEP) has been Studied since mid 1960's. While the original interest stemmed from geology applications (frost heaving in soil), it was recognized early that understanding particle behavior at solidifying interfaces mi ht yield 9 practical benefits in other fields. In metallurgical applications the issue is the location of particles with respect to grain boundaries at the end of solidification. Considerable amount of experimental and theoretical research was lately focused on applications to metal matrix composites produced by casting; or spray forming techniques. Another application of PEP is in the growing of Y1Ba2CU3O7-delta(123) superconductor crystals from an undercooled liquid. The oxide melt contains Y2Ba1CU1O5 (211) precipitates, which act as flux pinning sites. The paper presents results of PEP micro-gravity research performed by the authors on two shuttle missions using metallic and polymeric materials. In addition. a discussion on the theoretical aspects of the physics of PEP is offered. Analytical and numerical models for planar solidification interfaces developed by the authors are used to explain the experimental results. Shortcomings of steady-state models are emphasized. A numerical model that includes the effect of the solutal field and of natural convection is introduced. A discussion of phenomena associated with dendritic solidification based on experimental observations is also offered. A mechanism of engulfment is proposed.

Stefanescu, Doru M.↗
DOE OSTI2023

Computationally Guided Design of Multiple Impurities Tolerant Cathode for Solid Oxide Fuel Cell Applications

Solid oxide fuel cells (SOFCs) have been recognized as promising candidates in the demand of reducing the dependence on fossil fuels, which is one of the solutions to the threat of global warming. It was reported that the direct chemical-to-electrical energy conversion in SOFCs comes with negligible emission of greenhouse gases and up to 60% working efficiency. SOFC has unique advantages over traditional power generation technologies and other types of fuel cells due to the use of relatively inexpensive materials, low sensitivity to poisoning impurities in fuels, relatively high conversion efficiency, and fuel flexibility (like carbon-based fuels). However, during the SOFC operation, the cathode is exposed to intrinsic and extrinsic airborne contaminants at high temperatures (600–900°C), leading to their reaction with electrode materials, irreversible chemical and structural changes, and electrochemical performance degradation. of which CO2, SO2, Cr6+ and H2O are known to be concerns. Thus, developing a comprehensive understanding of the multiple impurities poisoning of SOFC cathodes in the presence of single or multiple impurities is necessary to address the long-term degradation of the SOFC cathode systems at operating conditions. An integrated computational and experimental approach has been utilized in the current work aiming at the comprehensive investigation of the cathode materials under single or multiple impurities poisoning effects, understanding the multiple impurities poisoning mechanism(s), and improving the long-term durability of the SOFC cathodes to develop better performing impurity-tolerant cathode materials. We first examined the agreement between the simulation approach and the experimental observations at various atmospheric and temperature conditions to confirm the reliability of CALPHAD for poisoning simulations in these cathodes. Then, using this approach, we investigated the accelerated testing protocol, which has become the standard method for conducting impurity poisoning experiments involving these cathode materials. We found our simulation approach is able to predict in which systems, i.e., cathode material and treatment environment, the accelerated testing protocols reflect actual operating conditions. Finally, in-depth simulations were done for these three candidate cathodes under different experimental conditions and suggested directions toward alternative cathode materials that have superior impurity tolerance.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Comparative Study of Zinc Cold-Spray Coating and Pre-treatments for Magnesium Alloys

Magnesium (Mg) alloys are appealing for automotive lightweighting owing to their high specific strength. However, their susceptibility to corrosion in harsh environments remains a major challenge. Conventional industrial pre-treatment coatings, including zinc phosphate, chromate conversion, and non-chromate conversion, often exhibit discontinuities and microcracks, leading to localized corrosion near fasteners and parting lines. Here, this study investigates cold-sprayed zinc (Zn) coatings as a novel pre-treatment alternative for high-pressure die cast (HPDC) AZ91 Mg alloys, demonstrating significant improvements in wear and corrosion performance. Cold spray produces uniform and robust coatings, reducing wear rate by over 50% and reducing corrosion rate by over 99.3%, as measured by evolved hydrogen release, compared to traditional pre-treatments. Multimodal corrosion testing reveals that Zn cold-spray coatings form a protective layer during exposure, minimizing general and filiform corrosion, and exhibiting corrosion potential (E corr ) that is nobler by ~ 400 mV than the surfaces of both pre-treated and uncoated AZ91. Scalability of cold spray for selective application around multimaterial joints further strengthens their industrial viability. This work establishes Zn cold-spray coatings as highly effective pre-treatment solutions for the advancement of corrosion resistant Mg alloy components in automotive applications.

multimodal corrosion↗
NASA NTRS2005

Control of Combustion-Instabilities Through Various Passive Devices

It is well known that under some operating conditions, rocket engines (using solid or liquid fuels) exhibit unstable modes of operation that can lead to engine malfunction and shutdown. The sources of these instabilities are diverse and are dependent on fuel, chamber geometry and various upstream sources such as pumps, valves and injection mechanism. It is believed that combustion-acoustic instabilities occur when the acoustic energy increase due to the unsteady heat release of the flame is greater than the losses of acoustic energy from the system [1, 2]. Giammar and Putnam [3] performed a comprehensive study of noise generated by gasfired industrial burners and made several key observations; flow noise was sometimes more intense than combustion roar, which tended to have a characteristic frequency spectrum. Turbulence was amplified by the flame. The noise power varied directly with combustion intensity and also with the product of pressure drop and heat release rate. Karchmer [4] correlated the noise emitted from a turbofan jet engine with that in the combustion chamber. This is important, since it quantified how much of the noise from an engine originates in the combustor. A physical interpretation of the interchange of energy between sound waves and unsteady heat release rates was given by Rayleigh [5] for inviscid, linear perturbations. Bloxidge et al [6] extended Rayleigh s criterion to describe the interaction of unsteady combustion with one-dimensional acoustic waves in a duct. Solutions to the mass, momentum and energy conservation equations in the pre- and post-flame zones were matched by making several assumptions about the combustion process. They concluded that changes in boundary conditions affect the energy balance of acoustic waves in the combustor. Abouseif et al [7] also solved the one-dimensional flow equations, but they used a onestep reaction to evaluate the unsteady heat release rate by relating it to temperature and velocity perturbations. Their analysis showed that oscillations arise from coupling between entropy waves produced at the flame and pressure waves originating from the nozzle. Yang and Culick [8] assumed a thin flame sheet, which is distorted by velocity and pressure oscillations. Conservation equations were expressed in integral form and solutions for the acoustic wave equations and complex frequencies were obtained. The imaginary part of the frequency indicated stability regions of the flame. Activation energy asymptotics together with a one-step reaction were used by McIntosh [9] to study the effects of acoustic forcing and feedback on unsteady, one-dimensional flames. He found that the flame stability was altered by the upstream acoustic feedback. Shyy et al [10] used a high-accuracy TVD scheme to simulate unsteady, one-dimensional longitudinal, combustion instabilities. However, numerical diffusion was not completely eliminated. Recently, Prasad [11] investigated numerically the interactions of pressure perturbations with premixed flames. He used complex chemistry to study responses of pressure perturbations in one-dimensional combustors. His results indicated that reflected and transmitted waves differed significantly from incident waves.

Frendi, Kader↗
DOE OSTI2020

At-source Recovery of Rare Earth Elements from Coal Mine Drainage

Conventional acid mine drainage (AMD) treatment consists of pH adjustment, oxidation, and separation of solid precipitates from discharge quality water. Alkaline addition increases the pH to the range 7 to 9 to precipitate the regulated metals Al and Mn ions as hydroxides. Mechanical or chemical oxidation then converts the reduced iron species Fe 2+ to Fe 3+ which precipitates at a low pH value as ferric hydroxide (Fe(OH) 3 ). Co-precipitation of Rare Earth Elements (REEs) with hydroxides creates a gangue-rich matrix from which REEs must be separated. Fe(OH)3 is generally the most abundant gangue-forming metal. Current research by the project team has shown raw, untreated AMD has an average total rare earth element content (TREE) of about 287 μg/L (0.287 ppm). Operators of AMD-producing facilities are obliged to treat it to neutralize acidity and remove regulated metals (e.g., iron (Fe), aluminum (Al), and manganese (Mn)) prior to discharge. Ongoing research indicates conventional AMD treatment concentrates TREE in resulting precipitates (AMD sludge) by an average factor of 2,635x to an average dry weight, elemental concentration of 708 g/t (ppm). While the economics of recovering REEs from AMD sludge are appealing, much of the cost of REE recovery would be incurred during separation of REEs from the gangue metals: Fe, Al, and Mn. Significant gains can be made by precipitating REEs when most of these gangue metals are still in solution. Significant improvements in REE extraction efficiency can be obtained through separation of REEs from the aqueous phase AMD, upstream of conventional AMD treatment by: 1) creating an enriched REE feedstock, 2) producing a more consistent feedstock, 3) reducing transportation costs to an REE refinery, 4) reducing acid consumption in the acid leaching step, and 5) reducing the volume of waste produced at the ALSX plant. This project is exploring two novel approaches for extracting REEs upstream of the conventional AMD treatment plants to create a purified REE feedstock while leaving the bulk of the Fe, Al, and Mn in solution for subsequent treatment. While the average TREE concentration of raw AMD is low and individual sites range between 10 and 2,200 μg/L, successful at-source REE separation will generate a superior feedstock to a conventional ALSX process and significantly improve the economics and environmental performance of REE extraction from AMD. AMD can be classified into two types: type A is net acid and iron is partly oxidized while type B is net alkaline, and iron occurs in the reduced, ferrous state. In Case A, the pH is raised slightly, which will precipitate Fe 3+ and Al 3+ but not REEs. The other important type of AMD is net alkaline water found in flooded, anoxic deep mines. These generally have a pH > 6.0 and are net alkaline. REE concentrations are also much lower than those found in acidic AMD while the volumes and flux are much higher. Most of these are pumped discharges with almost no Al. Case B AMD is strongly reduced and, like Case A water, Fe and Mn ions are similarly reduced and therefore soluble at pH <9.0. REEs and an array of transition ions will be the only trivalent cations in this type of AMD. In Case B, both upward pH adjustment under reducing conditions and application of an electrochemically stimulated supported liquid membrane strategy to separate REEs from ferrous ion will be explored.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

The ultrafast Kerr effect in anisotropic and dispersive media

The ultrafast optical Kerr effect (OKE) is widely used to investigate the structural dynamics and interactions of liquids, solutions, and solids by observing their intrinsic nonlinear temporal responses through nearly collinear four-wave mixing. Non-degenerate mixing schemes allow for background free detection and can provide information on the interplay between a material’s internal degrees of freedom. Here, we show a source of temporal dynamics in the OKE signal that is not reflective of the internal degrees of freedom but arises from a group index and momentum mismatch. It is observed in two-color experiments on condensed media with sizable spectral dispersion, a common property near an optical resonance. In particular, birefringence in crystalline solids is able to entirely change the character of the OKE signal via the off-diagonal tensor elements of the nonlinear susceptibility. We develop a detailed description of the phase-mismatched ultrafast OKE and show how to extract quantitative information on the spectrally resolved birefringence and group index from time-resolved experiments in one and two dimensions.

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

Adiabatic quantum decoherence in many non-interacting subsystems induced by the coupling with a common boson bath

Highlights: • System–environment quantum correlation: a main solid state NMR decoherence channel. • Non-separable system–environment model yields realistic spin decoherence rates. • New open quantum system approach explains irreversible decay of refocused NMR echoes. • Adiabatic quantum decoherence is inherently irreversible and eigen-selective. This work addresses adiabatic quantum decoherence of many-body spin systems coupled with a boson field in the framework of open quantum systems theory. We generalize the traditional spin-boson model by considering a system–environment interaction Hamiltonian that represents a partition of non-interacting subsystems and highlights the collective correlation that appears exclusively due to the coupling with a common environment. Remarkably, this simple, exactly solvable model encompasses relevant aspects of a many-body open quantum system and features the subtle quantum effects that arise when the size scales up to a macroscopic level. We derive an analytical expression for the time dependence of the density matrix elements (in the preferred basis) without assuming coarse-graining. The resulting decoherence function is eigen-selective and is a complex exponential whose exponent has a real part that introduces a decay similar to that in the spin-boson model. On the contrary, the imaginary part depends on the quantum numbers and geometry of the whole partition and does not reflect the system temperature. Motivated by decoherence in solid-state NMR, and in search of realistic numerical estimations, we apply the theoretical results to a partition of dipole-coupled spin pairs in contact with a common phonon bath, using typical parameters of hydrated salts. The proposal allows estimating the decoherence time scale in terms of the system physical constants: sound velocity and eigenvalue distribution width. As a significant novelty, the decoherence function phase depends on the eigenvalue distribution throughout the sample. It plays the leading role, overshadowing the mechanism associated with the bath thermal state. Finally, we apply the formalism to describe decoherence in the “magic echo” NMR reversal experiment. We find that the system–environment correlation explains the origin of irreversibility, and both the decoherence rate value and its dependence on the dipolar frequency, are remarkably similar to the experiment.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Atomic-Scale Insights into Carbon Dissolution in α-, γ-, and θ-Al 2 O 3 : Phase-dependent Transport Dynamics from First-Principles Calculations

α-Al 2 O 3 exhibits superior carburizing corrosion resistance compared to metastable γ-Al 2 O 3 and θ-Al 2 O 3 phases in high-temperature CO 2 environments, yet its atomic-scale origins remain unclear. Using first-principles density functional theory, we systematically investigate carbon dissolution and diffusion in α-Al 2 O 3 , γ-Al 2 O 3 , and θ-Al 2 O 3 , including the effects of oxygen (O) and aluminum (Al) vacancies. Our results show that α-Al 2 O 3 consistently exhibits higher carbon solution enthalpies than γ-Al 2 O 3 and θ-Al 2 O 3 in both pristine and defective structures, indicating lower intrinsic carbon solubility in α-Al 2 O 3 . Vacancies significantly enhance carbon incorporation: O vacancies reduce solution enthalpy, while Al vacancies further amplify this effect, with a strong preference for carbon at Al vacancy sites. Carbon diffusion barriers are also highest in α-Al 2 O 3 , reflecting slower carbon mobility. Al vacancies increase diffusion barriers across all phases, while O vacancies raise barriers in α- and γ-Al 2 O 3 but slightly lower them in θ-Al 2 O 3 . These results reveal a dual mechanism behind the carburizing resistance of α-Al 2 O 3 : reduced carbon solubility and elevated diffusion barriers. Furthermore, this work provides atomic-scale insights to guide the design of alumina-based materials with improved carburizing resistance through phase selection and defect engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Accelerating the Discovery of New, Single Phase High Entropy Ceramics via Active Learning

High-entropy ceramics have garnered interest due to their remarkable hardness, compressive strength, thermal stability, and fracture toughness; yet the discovery of new high-entropy ceramics (out of a tremendous number of possible elemental permutations) still largely requires costly, inefficient, trial-and-error experimental and computational approaches. The entropy forming ability (EFA) factor was recently proposed as a computational descriptor that positively correlates with the likelihood that a 5-metal high-entropy carbide (HECs) will form the desired single phase, homogeneous solid solution; however, discovery of new compositions is computationally expensive. If you consider 8 candidate metals, the HEC EFA approach uses 49 optimizations for each of the 56 unique 5-metal carbides, requiring a total of 2744 costly density functional theory calculations. Here, we describe an orders-of-magnitude more efficient active learning (AL) approach for identifying novel HECs. To begin, we compared numerous methods for generating composition-based feature vectors (e.g., magpie and mat2vec), deployed an ensemble of machine learning (ML) models to generate an average and distribution of predictions, and then utilized the distribution as an uncertainty. Here we then deployed an AL approach to extract new training data points where the ensemble of ML models predicted a high EFA value or was uncertain of the prediction. Our approach has the combined benefit of decreasing the amount of training data required to reach acceptable prediction qualities and biases the predictions toward identifying HECs with the desired high EFA values, which are tentatively correlated with the formation of single phase HECs. Using this approach, we increased the number of 5-metal carbides screened from 56 to 15,504, revealing 4 compositions with record-high EFA values that were previously unreported in the literature. Our AL framework is also generalizable and could be modified to rationally predict optimized candidate materials/combinations with a wide range of desired properties (e.g., mechanical stability, thermal conductivity).

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Integrated Design Results for the MSR DAC-0.0 Mars Ascent Vehicle

The NASA Mars Sample Return (MSR) Campaign endeavors to return Martian regolith, rock, and atmospheric samples to Earth for scientific study. One of many significant challenges to overcome in the return of these samples lies in transporting them from the Martian surface to space. In order to surmount this challenge, the Campaign has conceptualized the need for a Mars Ascent Vehicle (MAV) to perform this function and deliver Martian samples to orbit. There, the samples will be ejected and captured by a separate spacecraft for return to Earth. Many concepts for a MAV have existed in the past, but it has not been until now that an integrated, detailed design solution has been developed and analyzed. Preliminary assessments of the initial architecture examined multiple methods of propulsion. The team ultimately determined that a Two Stage to Orbit (TSTO) solid propulsion vehicle would provide the most effective performance and be the most technologically ready to support this mission. Following the decision to adopt a TSTO solid propelled vehicle, the first official Design Analysis Cycle, DAC-0.0, was performed in Spring 2020 to formally advance the fidelity of the vehicle to a maturity level acceptable for NASA Key Decision Point A (KDP-A). This paper describes the resultant MAV design concept developed as part of the DAC-0.0 study by the NASA Marshall Space Flight Center (MSFC), in association with the NASA Jet Propulsion Laboratory (JPL). The TSTO vehicle features two solid rocket motors, one powering each stage. Their thrust vectors are controlled with Thrust Vector Control (TVC) systems consisting of independent electromechanical actuators acting on gimballed nozzles. The vehicle is designed to deliver up to 0.47kg of Martian samples to a Mars circular orbit of 343km at 27° inclination. Due to the unique environmental conditions that this vehicle is required to operate in, the subsystem design teams were compelled to develop creative and unorthodox designs to ensure a successful mission. The detailed design and analysis of these subsystems are discussed in this paper and include topics on the MAV Guidance, Navigation, and Control (GNC); structures and mechanisms; integrated vehicle thermal; avionics and flight software; a hydrazine-based Reaction Control System (RCS); aerosciences; and vehicle assembly, integration, and test (AI&T) considerations, among others. Following the conclusion of the MAV DAC-0.0, additional alternative architecture concepts were also studied to further reduce the mass of the overall system. The results of these studies will also be examined in this paper.

Darius Yaghoubi↗
NASA NTRSDate not supplied

Integrated Design Results for the MSR DAC-0.0 Mars Ascent Vehicle

The NASA Mars Sample Return (MSR) Campaign endeavors to return Martian regolith, rock, and atmospheric samples to Earth for scientific study. One of many significant challenges to overcome in the return of thesesamples lies in transporting them from the Martian surface to space. In order to surmount this challenge, the Campaign has conceptualized the need for a Mars Ascent Vehicle (MAV) to perform this function and deliver Martian samples to orbit. There, the samples will be ejected and captured by a separate spacecraft for return to Earth. Many concepts for a MAV have existed in the past, but it has not been until now that an integrated, detailed design solution has been developed and analyzed. Preliminary assessments of the initial architecture examined multiple methods of propulsion. The team ultimately determined that a Two Stage to Orbit (TSTO) solid propulsion vehicle would provide the most effective performance and be the most technologically ready to support this mission. Following the decision to adopt a TSTO solid propelled vehicle, the first official Design Analysis Cycle, DAC-0.0, was performed in Spring 2020 to formally advance the fidelity of the vehicle to a maturity level acceptable for NASA Key Decision Point A (KDP-A). This paper describes the resultant MAV design concept developed as part of the DAC-0.0 study by the NASA Marshall Space Flight Center (MSFC), in association with the NASA Jet Propulsion Laboratory (JPL). The TSTO vehicle features two solid rocket motors, one powering each stage. Their thrust vectors are controlled with Thrust Vector Control (TVC) systems consisting of independent electromechanical actuators acting on gimballed nozzles. The vehicle is designed to deliver up to 0.47kg of Martian samples to a Mars circular orbit of 343km at 27° inclination. Due to the unique environmental conditions that this vehicle is required to operate in, the subsystem design teams were compelled to develop creative and unorthodox designs to ensure a successful mission. The detailed design and analysis of these subsystems are discussed in this paper and include topics on the MAV Guidance, Navigation, and Control (GNC); structures and mechanisms; integrated vehicle thermal; avionics and flight software; a hydrazine-based Reaction Control System (RCS); aerosciences; and vehicle assembly, integration, and test (AI&T) considerations, among others. Following the conclusion of the MAV DAC-0.0, additional alternative architecture concepts were also studied to further reduce the mass of the overall system.

Mars↗