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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 325 records · Page 18

Electrochemical control over stoichiometry via cation intercalation into Chevrel-phase sulphides (Cu x Mo 6 S 8 , x = 1-3)

Herein this work presents a systematic investigation of the electrochemical intercalation of aqueous copper cations into the Chevrel phase (CP) Mo 6 S 8 and its effect on the host's electronic and structural characteristics as a function of stoichiometry. The electrochemical potentials at which copper intercalates into the CP Mo 6 S 8 host in 1 M CuSO 4 were identified for Cu x Mo 6 S 8 (x = 1–3) as 0.23 V, 0.11 V, and 0.055 V (vs. Cu/Cu 2+ ) for Cu 1 Mo 6 S 8 , Cu 2 Mo 6 S 8 , and Cu 3 Mo 6 S 8 , respectively, and correlated via ex situ PXRD to stoichiometric content. Potentials were also identified that yield non-stoichiometric phases with traceable Cu content-dependent structural changes. Ab initio DFT calculations were performed to probe thermodynamic stability of Cu x Mo 6 S 8 CP compositions and the metal-to-semiconductor transitions as a function of copper content. Lastly, we demonstrate that the SK-pre-edge intensity is a successful probe for intercalant content: as copper equivalents increase, so does charge transfer to the partially occupied S 3p orbitals, resulting in a decrease in the pre-edge intensity corresponding to the excitation of a S 1s-to-3p/Mo 4d hybridized orbital.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructure and magnetization of doped Y-Ba-Ca-O materials prepared by melt quench and post annealing method

Y-Ba-Cu-O bulk materials prepared using the melt quench and post annealing method were shown to have very high maximum as well as remanent magnetization. Studies were carried out on materials prepared using this method which deviate from the Y:Ba:Cu = 1:2:3 stoichiometry. In one series of materials, only the stoichiometry was changed, in particular by introducing an excess of yttrium. In other cases, dopants including several rare earths were introduced. Effects of variations in composition on microstructure and phase evolution are discussed, as well as effects on the magnetic susceptibility and on the magnetization. The results show that doped materials can exhibit improvements in magnetic properties. Furthermore, the use of dopants sheds light on the role of defect sites in flux pinning.

Hojaji, H.↗

Dopant Studies in the BaCe0.9-xZrxY0.103- System

Protonic separation membranes for the hydrogen industry require thermo-chemical stability and high conductance. The perovskite BaCe0.9Y0.1O3- exhibits excellent proton conduction at high temperatures, but shows poor thermo-chemical tability. Substituting Zr for Ce in BaZr0.9Y0.1O3- improves the thermo-chemical stability but reduces proton conduction. The objective of this work was to study the optimization of protonic conductance and thermo-chemical by changing the ratio of Ce to Zr in BaCe0.9-xZrxY0.1O3-. To elucidate the dopant effect, co-precipitation method has been developed to produce single phase perovskites of composition BaCe0.9-xZrxY0.1O3- (0=x=0.9). The co-precipitation method has been optimized to yield high purity and homogeneous powders with a particle size of 100-200 nm in diameter. The sintering characteristics were studied in temperature range of 1400-1600 C. The effect of Zr substitution on sintering behavior and thermo-chemical stability will be reported.

Zhong, Zhimin↗

Mesoporous Silicon-Based Anodes

For high-capacity, high-performance lithium-ion batteries. A new high-capacity anode composite based on mesoporous silicon is being developed. With a structure that resembles a pseudo one-dimensional phase, the active anode material will accommodate significant volume changes expected upon alloying and dealloying with lithium (Li).

Peramunage, Dharmasena↗

Design and Analysis of Battery Thermal Management Systems

Thermal management of battery cell packs is a critically needed technology. The purpose of this work is to design new and improved Battery Thermal Management Systems (BTMS) for use in electric airplanes. The BTMS should be 3D printable and hold twelve to sixteen 18650 batteries. To minimize aircraft’s weight, an actively air-cooled battery pack was chosen to avoid the excess weight of water-cooled and phase change material (PCM) cooled packs. As a result, significant changes were made to remove all metal in the pack and replace it with lower density polymer matrix composites (PMCs) which can be additively manufactured. Two air cooled battery pack configurations (traditional propeller fans & bladeless fans) were designed, modeled, and compared. These packs were first modeled in SolidWorks 2021 3D CAD, then imported into COMSOL MultiPhysics to be studied using the “Heat Transfer in Solids and Fluids” module. The design with the bladeless fans eliminated the need to use high conductivity heavy metal to remove unwanted thermal energy. These bladeless fans were designed entirely out of PMCs. This thermal pack design weighs 0.04 kg less than that of the traditional propeller fans design and has increased the battery pack energy density by 8.25 Wh/kg.

Thermal Management System for Battery Packs↗

Computational Fluid Dynamics Simulation of Methane Slosh and Drain Experiments

NASA possesses a wealth of historical cryogenic experiments that provide valuable insights into the design, troubleshooting, and understanding involved in the complex fluid and thermodynamics of managing cryogenic propellants. One approach to leveraging these historical datasets is by simulating these experiments to validate the accuracy of simulation environments and constituent models. This study focused on simulating a selection of the K site test series for both static and sloshing pressurized liquid methane draining experiments conducted at NASA in the 1970’s, utilizing computational fluid dynamics. The simulations were performed in the ANSYS FLUENT environment using the Volume of Fluid (VOF) numerical approach. A k-omega turbulence model was used with interfacial turbulence damping, and accurately predicted the amount of pressurant needed to maintain the required tank pressure throughout the static drain. The static simulation predicted the temperature stratification in the ullage observed at the end of the drain. During the methane expulsion with sloshing test, many features were successfully captured using the k-omega turbulence model with interfacial turbulence damping included. The rate of phase change and liquid temperature was overpredicted compared to the experimental measurements. The overprediction may be attributed to uncertainties in the vessel geometry, methane pressurant temperature and composition, and methodological differences in how the sloshing frequency was adjusted during the expulsion.

Cryogenic Propellants↗

Thermal Effects on a Low Cr Modification of PS304 Solid Lubricant Coating

PS304 is a high temperature composite solid lubricant coating composed of Ni-Cr, Cr2O3, BaF2-CaF2 and Ag. The effect of reducing chromium content on the formation of voids in the Ni-Cr particles after heat treatment in PS304 coating was investigated. Coatings were prepared with Ni-20Cr or Ni-10Cr powder and in various combinations with the other constituents of PS304 (i.e., chromia, silver and eutectic BaF2-CaF2 powders) and deposited on metal substrates by plasma spray. Specimens were exposed to 650 C for 24 hr or 1090 C for 15 hr and then examined for changes in thickness, coating microstructure and adhesion strength. Specimens with Ni-10Cr generally had less thickness increase than specimens with Ni-20Cr, but there was great variance in the data. Reduction of chromium concentration in Ni-Cr powder tended to reduce the appearance of voids in the Ni-Cr phase after heat exposure. The presence of BaF2-CaF2 resulted in a significant increase in coating adhesion strength after heat treatment, while coatings without BaF2-CaF2 had no significant change. Chemical composition analysis suggested that the void formation was due to oxidation of chromium in the Ni-Cr constituent.

Stanford, Malcolm K.↗

Geometric control of magnetic domain morphology in electrodeposited Ni rich NiPt mesoscopic wires

In this paper, we study the electrodeposited Ni—Pt magnetic wires, exploring the mechanisms by which changes in geometry and composition influence the local magnetic structure. The samples were prepared by electrodeposition, their elemental composition was analyzed by energy dispersive X-ray spectroscopy, and phase analysis was carried out by an X-ray diffraction measurement. Magnetic force microscopy measurements, and magnetic force microscopy measurements in magnetic field were carried out to study the domain morphology of the prepared samples. Magnetization characteristics were measured via vibrating sample magnetometry mode of a superconducting quantum interference device. Here, the results were analyzed and compared with micromagnetic simulations. It is shown that a strong perpendicular magnetic anisotropy is responsible for the characteristic checkerboard-like surface magnetization patterns, which can be tuned by geometrical constriction and Ni content. Understanding these relationships provides insights into the design of magnetic materials with tailored properties for advanced applications, like magnetic sensors.

Binary alloy↗

The Composition of Amorphous Phases in Soils and Sediments on Earth and Mars

Amorphous phases are major components (~15-70 wt%) of all rock and soil samples measured thus far by the CheMin X-ray diffractometer (XRD) instrument on the MSL rover in Gale crater, Mars. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., silica, errihydrite) phases. Secondary amorphous phases are frequently found as weathering products in soils on Earth, but these materials remain poorly characterized, and it is not certain how properties like composition and structure change with formation environment.

Smith, R. J.↗

Effect of chromium on corrosion resistance of Ni-Cr-Mo-Gd alloys in seawater

Neutron absorbing materials are being considered within commercial spent nuclear fuel disposal canisters to maintain nuclear subcriticality in storage. To select candidate alloys for the canisters, both neutron absorption and corrosion resistance should be considered. This work examines corrosion resistance of Ni-Cr-Mo-Gd alloys developed specifically for neutron absorption. The addition of Gd results in a secondary gadolinide phase (Ni 5 Gd) that significantly changes the corrosion properties. Testing was performed primarily in seawater at 30°C. Seawater was selected as the most prevalent terrestrial brine and is characterized by a high chloride concentration. Various electrochemical corrosion techniques were carried out to evaluate Ni-Cr-Mo-Gd alloys with different Cr compositions and investigate the role of Ni 5 Gd phase on corrosion behavior. C22 was included as a benchmark material, due to the similarity in composition and the significant corrosion data available. Here, test results showed a tendency to passivate over time which is attributed to dissolution of surface exposed Ni 5 Gd phase. Cross-sectional analysis indicated that dissolution could penetrate hundreds of micrometers deep under aggressive conditions. It was found that higher Cr variant (21.01%) showed much shallower impact, suggesting Cr prevented primary phase corrosion and thus reduced Ni 5 Gd phase dissolution. Acid pickling of the specimens showed much less dissolution for a higher Cr material and suggested some primary phase dissolution for the low Cr specimen. Acid pickled specimens showed positive shifts in the repassivation potential, suggesting increased surface passivation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mixing Matters: Nanoscale Heterogeneity and Stability in Metal Halide Perovskite Solar Cells

The structural stability of the metal halide perovskite (MHP) absorber material is crucial for the long-term solar cell stability in this thin-film photovoltaic technology. Here, we use mixed A-site FA0.83Cs0.17PbI3 to demonstrate that nanoscale compositional heterogeneity can serve as initiation sites for more macroscale, irreversible phase segregation, which causes device performance degradation. Probing compositional heterogeneity on length scales that has not been detected with conventional characterization techniques, we analyze the tetragonal to cubic phase transition behavior to indirectly determine the level of nanoscale compositional heterogeneity in the initial films. Further, we show that the thermal annealing conditions of the MHP layer during film processing influence the initial nanoscale compositional heterogeneity, and changing these processing conditions can be used to improve the device performance stability. The insights into structural degradation mechanisms initiated by nanoscale compositional heterogeneity and the proposed mitigation strategies will help guide the way toward long-term stable MHP solar cells.

14 SOLAR ENERGY↗

Parameterized materials and dynamic response characterizations in unidirectional composites

The values of phase velocities of ultrasonic waves in transversely isotropic media are presented in terms of the fiber volume fraction of a unidirectional fiberglass epoxy composite with constant matrix properties and the ratio between extensional moduli in the longitudinal and transverse directions of the composite when the properties of the fibers are changed, at a constant fiber volume fraction. The model of a homogeneous transversely isotropic medium is adopted to describe the relations between elastic properties and velocities. The displacements due to an oscillatory point source in an infinite medium are used as one measure of comparison of the behavior of the unidirectional composite according to the variations of the parameters, as described above. Values of phase velocities, elastic moduli, Poisson's ratios and displacements due to a point source can be read from the parameterized plots for a known fiber volume fraction or a known ratio between extensional moduli of the composite. Alternatively fiber volume fraction and the ratio between extensional moduli can be inferred from the plots when the values of the phase velocities are known; for example from experimental measurements. Therefore, such parameterized curves may be useful in nondestructive mechanical property and material degradation characterizations.

Williams, J. H., Jr.↗

Development of Stable Solid Oxide Electrolysis Cells for Low-Cost Hydrogen Production

The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .

08 HYDROGEN↗

Transmission Electron Microscopy Study on the Effect of Thermal and Electrical Stimuli on Ge2Te3 Based Memristor Devices

Memristor devices fabricated using the chalcogenide Ge 2 Te 3 phase change thin films in a metal-insulator-metal structure are characterized using thermal and electrical stimuli in this study. Once the thermal and electrical stimuli are applied, cross-sectional transmission electron microscopy (TEM) and X-ray energy-dispersive spectroscopy (XEDS) analyses are performed to determine structural and compositional changes in the devices. Electrical measurements on these devices showed a need for increasing compliance current between cycles to initiate switching from low resistance state (LRS) to high resistance state (HRS). The measured resistance in HRS also exhibited a steady decrease with increase in the compliance current. High resolution TEM studies on devices in HRS showed the presence of residual crystalline phase at the top-electrode/dielectric interface, which may explain the observed dependence on compliance current. XEDS study revealed diffusion related processes at dielectric-electrode interface characterized, by the separation of Ge 2 Te 3 into Ge- and Te- enriched interfacial layers. This was also accompanied by spikes in O level at these regions. Furthermore, in-situ heating experiments on as-grown thin films revealed a deleterious effect of Ti adhesive layer, wherein the in-diffusion of Ti leads to further degradation of the dielectric layer. This experimental physics-based study shows that the large HRS/LRS ratio below the current compliance limit of 1 mA and the ability to control the HRS and LRS by varying the compliance current are attractive for memristor and neuromorphic computing applications.

Shallcross, Austin↗

Valence State Partitioning of Cr and V Between Olivine-Melt and Pyroxene-Melt in Experimental Basalts of a Eucritic Composition

The partitioning of multivalent elements in basaltic systems can elucidate the oxygen fugacity (fO2) conditions under which basalts formed on planetary bodies (Earth, Moon, Mars, asteroids). Chromium and V are minor and trace elements in basaltic melts, partition into several minerals that crystallize from basaltic melts, exist in multiple valence states at differing fO2 conditions, and can therefore be used as oxybarometers for basaltic melts. Chromium is mostly 3+ in terrestrial basaltic melts at relatively high fO2 values (≥ IW+3.5), and mostly 2+ in melts at low fO2 values (≤ IW-1), such as those on the Moon and some asteroids. At intermediate fO2s, (i.e., IW-1 to IW+3.5), basaltic melts contain both Cr3+ and Cr2+. Vanadium in basaltic melts is mostly 4+ at high fO2, mostly 3+ at low fO2, and a mix of V3+ and V4+ at intermediate fO2 con-ditions. Understanding the partitioning of Cr and V into silicate phases with changing fO2 is therefore critical to the employment of Cr and V oxybarometers. In this abstract we examine the equilibrium partitioning of Cr and V between olivine/melt and pyroxene/melt in experimental charges of a eucritic composition produced at differing fO2 conditions. This study will add to the experimental data on DCr and DV (i.e., olivine/melt, pyroxene/melt) at differing fO2, and in turn these D values will be used to assess the fO2 of eucrite basalts and perhaps other compositionally similar planetary basalts.

Karner, J. M.↗

An Integrated Computational Materials Engineering (ICME) Approach to Design Nonlinear Transition Zones Between Dissimilar Metals

Current approaches to designing graded transition joints (GTJs) between dissimilar metals often rely on linear changes in both composition profiles and thickness of each sublayer. This increases fabrication cost and may not be optimal with respect to residual stress or the formation of undesirable phases. Here, in this study, GTJs between P91 ferritic/martensitic steel and 347H austenitic stainless steel were designed using Integrated Computational Materials Engineering (ICME) principles with nonlinear composition and length profiles. Guided by inputs from classical mechanics and CALPHAD predictions of carbon chemical potential, a novel transition zone consisting of five discrete compositions was proposed, with the thickness of each sublayer varying according to a brachistochrone-inspired distribution. In addition to carbon potential gradients, CALPHAD was used to predict coefficients of thermal expansion, which were incorporated into finite element models to evaluate stress evolution. The proposed nonlinear design resulted in a smoother carbon potential gradient, lower carbon depletion at the P91 interface, and a comparable residual stress under long-term thermal exposure, compared to a conventional linear design using ten sublayers with equal thickness. This work introduces a brachistochrone-inspired distribution for GTJ design, offering a general framework for optimizing graded interfaces between dissimilar metals.

Directed Energy Deposition↗

Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ 34 S records

We report total reduced inorganic S isotope ratios (δ 34 S CRS ) shift toward more negative values across much of the southern North Atlantic just before the onset of the Cenomanian-Turonian Ocean Anoxic Event (OAE-2). At the same time, there is no parallel isotopic change in the significantly larger pool of kerogen (organic) S, which indicates that the distribution and S-isotope composition of sulfide in the environment likely did not drive the change in δ 34 S CRS . Here, we investigate possible explanations for the negative shift in δ 34 S CRS values and their divergence from organic S by isolating iron sulfides for morphological identification and grain-specific isotopic analysis using secondary ion mass spectrometry (SIMS). In pre- and syn-OAE-2 sedimentary rocks from Demerara Rise, we find four distinct morphologies of iron sulfides: pyrite framboids (1–20 μm diameter), irregular pyrite aggregates (1–38 μm diameter), large cemented pyrite aggregates (~60 μm diameter), and irregular and cemented aggregates of the pyrite polymorph marcasite (1–45 μm diameter). These different textural groups have distinct S-isotopic compositions that are largely consistent through the onset of OAE-2. As such, the secular change in bulk δ 34 S CRS values likely reflects the changing proportions of these phases stratigraphically across OAE-2. All textural groups feature resolvable intra-grain δ 34 S variability, suggesting that the environments in which they formed were characterized by dynamic sulfide δ 34 S values and/or by partial closed-system distillation. We use grain-specific δ 34 S distributions to rule out shoaling of the chemocline within the sediments as a mechanism for the observed decrease in δ 34 S CRS . Instead, we propose that changes in the reactivity of the iron species delivered to Demerara Rise over the ~200 kyr leading up to the onset of OAE-2 impacted the relative contributions of pyrite with S-isotope signatures reflecting the water column, shallow sediments, and deeper sediments to the bulk sedimentary δ 34 S CRS value. Specifically, the change in iron reactivity at the onset of OAE-2 favored the production of 34 S-depleted large, cemented aggregates and framboids at the expense of more 34 S-enriched irregular aggregates. Our results underscore that bulk δ 34 S CRS measurements integrate multiple reduced phases that form via distinct reaction mechanisms and potentially in different parts of the depositional environment. Grain-specific SIMS analyses dramatically enrich our ability to interpret pyrite isotopic patterns in the geologic record.

58 GEOSCIENCES↗

Magnetocaloric effect in Mn-rich Heusler-derived alloys for room temperature-based applications

Magnetic refrigeration-based technologies rely on the magnetocaloric properties of materials and are crucial for improving energy efficiency and for supporting clean environments. However, materials possessing significant magnetocaloric properties that can be used for room temperature-based applications are still lacking. Heusler alloys (such as Mn–Ni–Ga) show giant magnetocaloric effects, which can be further improved by tuning their composition. Herein, we optimized the ratio of Ni to Ga to achieve an alloy with unique magnetocaloric properties. Here, the alloy demonstrated a substantial magnetocaloric effect, attributed to its narrow temperature range for structural and magnetic phase transitions (near room temperature with minimal hysteresis). Structural phase changes were also observed through high-resolution transmission electron microscopy. Optimum entropy changes, calculated from isothermal magnetization curves (4 Tesla magnetic field), were found to be 24.50 J kg −1 K −1 , which is higher than that of state-of-the-art alloys. Experimental demonstration of the magnetocaloric effect (refrigeration cycle) was also carried out using a thermal imaging camera. Furthermore, first-principles calculations were conducted to validate the experimental findings, specifically focusing on the compositional effects on the structural transitions and magnetic properties of the investigated MNG alloys.

36 MATERIALS SCIENCE↗