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Metal matrix composites microfracture - Computational simulation

Fiber/matrix fracture and fiber-matrix interface debonding in a metal matrix composite (MMC) are computationally simulated. These simulations are part of a research activity to develop computational methods for microfracture, microfracture propagation and fracture toughness of the metal matrix composites. The three-dimensional finite element model used in the simulation consists of a group of nine unidirectional fibers in three by three unit cell array of SiC/Ti15 metal matrix composite with a fiber volume ration of 0.35. This computational procedure is used to predict the fracture process and establish the hierarchy of fracture modes based on strain energy release rate. It is also used to predict stress redistribution to surrounding matrix-fibers due to initial and progressive fracture of fiber/matrix and due to debonding of fiber-matrix interface. Microfracture results for various loading cases such as longitudinal, transverse, shear and bending are presented and discussed. Step-by-step procedures are outlined to evaluate composite microfracture for a given composite system.

Mital, S. K.↗

Finite-element boundary-integral simulation of thin wires and inhomogeneous penetrable bodies in subsurface multilayered anisotropic media

With the prevailing presence of drilling wells near the subsurface in mature oil and gas fields, the application of electromagnetic methods can be particularly challenging where the electromagnetic field is affected by the steel casing. In the past decades, borehole-to-surface and crosswell electromagnetic methods have been utilized for monitoring of reservoir and underground CO 2 storage. This paper presents a unified finite-element boundary-integral (FEBI) method capable of simultaneously modeling the complex electromagnetic interactions between thin metallic wires (representing steel casings) with 3D trajectory and arbitrary 3D inhomogeneous penetrable bodies (such as CO 2 plumes or hydrocarbon reservoirs) within anisotropic multilayered subsurface environments. Unlike existing approaches that treat these components separately or require dense discretization, or are limited to vertical wells, our unified formulation preserves flexible electromagnetic coupling while delivering improved computational efficiency. Assuming the background formation is multilayered anisotropic media, the surface integral equation method is applied to model the thin wires and boundaries of the inhomogeneous bodies. Meanwhile, the finite element method is applied to model the volume of inhomogeneous bodies. Here, the performance of the proposed FEBI method is assessed through comparison with reference numerical results and its practical significance is demonstrated through CO 2 plume monitoring scenarios.

97 MATHEMATICS AND COMPUTING↗

The Center for Performance and Design of Nuclear Waste Forms and Containers (WastePD) Energy Frontier Research Center (Final Report)

The DOE Office of Environmental Management is responsible for high level nuclear waste that must be safely isolated from humans and the environment for extremely long periods. The waste forms and containers are made of glass, ceramics, and metals. Verified safe disposal requires understanding the fundamental mechanisms of waste form degradation and the design of new waste forms with improved performance, which comprise the goals of the Energy Frontier Research Center known as the Center for the Performance and Design of Nuclear Waste Forms and Containers, WastePD. WastePD was constructed to develop innovative approaches and solutions to those goals through the synergistic interactions of individuals who are experts in the degradation behavior, modeling, and design of glasses, ceramics and metal alloys. WastePD is the first center ever created to address this diverse group of materials in a comprehensive and coordinated manner. The science goals are grouped into three common topics: corrosion mechanisms via advanced characterization, environmental impacts, and materials design. Synergistic interactions in these areas were a key component of WastePD. The fundamental understanding of the degradation mechanisms of the waste forms and containers as well as the development of new materials with improved properties will allow DOE to prevent environmental contamination and to explore totally new repository concepts. WastePD was operational from August 2016 through July 2022, but the DOE support was drastically reduced for the last two years. This final technical report covers the full period of performance. However, much of what was accomplished in the first four years is nicely summarized in a review paper published in 2021, which is appended to this report. Therefore, this final report focuses on the technical findings from the last two years of WastePD activities. Considerable progress was made in the areas of a) the environmental and compositional impacts on the corrosion of borosilicate and aluminosilicate glasses, b) the mechanism of glass corrosion and the structure and evolution of the surface alteration layer, c) the effects of environment and composition on the corrosion of pyrochlore, perovskite, hollandite, and other oxide ceramics, d) the corrosion mechanism of multi-principal element metallic alloys, and e) a new framework for understanding the pitting corrosion of metals.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

In Situ Determination of Speciation and Local Structure of NaCl–SrCl 2 and LiF–ZrF 4 Molten Salts

Understanding the local environment of the metal atoms in salt melts is important for modeling the properties of melts and predicting their behavior and thus helping enable the development of technologies such as molten salt reactors and solar-thermal power systems and new approaches to recycling rare-earth metals. Toward that end, we have developed an in situ approach for measuring the coordination of metals in molten salt coupling X-ray absorption spectroscopy (XAS) and Raman spectroscopy. Our approach was demonstrated for two salt mixtures (1.9 and 5 mol % SrCl 2 in NaCl, 0.8 and 5 mol % ZrF 4 in LiF) at up to 1100 °C. Near-edge (X-ray absorption near-edge structure, XANES) and extended X-ray absorption fine structure (EXAFS) spectra were measured. The EXAFS response was modeled using ab initio FEFF calculations. Strontium’s first shell is observed to be coordinated with chlorine (Sr 2+ –Cl – ) and zirconium’s first shell is coordinated by fluorine (Zr 4+ –F – ), both having coordination numbers that decrease with increasing temperature. Multiple zirconium complexes are believed to be present in the melt, which may interfere and distort the EXAFS spectra and result in an anomalously low zirconium first shell coordination number. Finally, the use of boron nitride (BN) powder as a salt diluent for XAFS measurements was found to not interfere with measurements and thus can be used for investigations of such systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design principles for self-forming interfaces enabling stable lithium-metal anodes

Significance It is possible to nearly double the energy density of existing lithium-ion batteries by using lithium metal anodes. However, it has been known for decades that the lithium dendrites and mossy lithium formed during charging (electrodeposition) limit the cycle life of the batteries. It is important to change the growth behavior of lithium metal, which is closely related to the properties of the solid–electrolyte interface (SEI) formed via spontaneous reactions between the lithium metal and the electrolyte. In this experimental-modeling integrated study, we reveal the design principles of the SEI that facilitates the dendrite-free and dense deposition of lithium and demonstrate one of the best cycling performances of lithium metal anode to date under practically relevant conditions.

25 ENERGY STORAGE↗

Development of a Computer Architecture to Support the Optical Plume Anomaly Detection (OPAD) System

The NASA OPAD spectrometer system relies heavily on extensive software which repetitively extracts spectral information from the engine plume and reports the amounts of metals which are present in the plume. The development of this software is at a sufficiently advanced stage where it can be used in actual engine tests to provide valuable data on engine operation and health. This activity will continue and, in addition, the OPAD system is planned to be used in flight aboard space vehicles. The two implementations, test-stand and in-flight, may have some differing requirements. For example, the data stored during a test-stand experiment are much more extensive than in the in-flight case. In both cases though, the majority of the requirements are similar. New data from the spectrograph is generated at a rate of once every 0.5 sec or faster. All processing must be completed within this period of time to maintain real-time performance. Every 0.5 sec, the OPAD system must report the amounts of specific metals within the engine plume, given the spectral data. At present, the software in the OPAD system performs this function by solving the inverse problem. It uses powerful physics-based computational models (the SPECTRA code), which receive amounts of metals as inputs to produce the spectral data that would have been observed, had the same metal amounts been present in the engine plume. During the experiment, for every spectrum that is observed, an initial approximation is performed using neural networks to establish an initial metal composition which approximates as accurately as possible the real one. Then, using optimization techniques, the SPECTRA code is repetitively used to produce a fit to the data, by adjusting the metal input amounts until the produced spectrum matches the observed one to within a given level of tolerance. This iterative solution to the original problem of determining the metal composition in the plume requires a relatively long period of time to execute the software in a modern single-processor workstation, and therefore real-time operation is currently not possible. A different number of iterations may be required to perform spectral data fitting per spectral sample. Yet, the OPAD system must be designed to maintain real-time performance in all cases. Although faster single-processor workstations are available for execution of the fitting and SPECTRA software, this option is unattractive due to the excessive cost associated with very fast workstations and also due to the fact that such hardware is not easily expandable to accommodate future versions of the software which may require more processing power. Initial research has already demonstrated that the OPAD software can take advantage of a parallel computer architecture to achieve the necessary speedup. Current work has improved the software by converting it into a form which is easily parallelizable. Timing experiments have been performed to establish the computational complexity and execution speed of major components of the software. This work provides the foundation of future work which will create a fully parallel version of the software executing in a shared-memory multiprocessor system.

Katsinis, Constantine↗

Multiphysics Modeling for Dimensional Analysis of a Self-Heated Molten Regolith Electrolysis Reactor for Oxygen and Metals Production on the Moon and Mars

The technology of direct electrolysis of molten lunar regolith to produce oxygen and molten metal alloys has progressed greatly in the last few years. The development of long-lasting inert anodes and cathode designs as well as techniques for the removal of molten products from the reactor has been demonstrated. The containment of chemically aggressive oxide and metal melts is very difficult at the operating temperatures ca. 1600 C. Containing the molten oxides in a regolith shell can solve this technical issue and can be achieved by designing a self-heating reactor in which the electrolytic currents generate enough Joule heat to create a molten bath.

Dominguez, Jesus↗

Unveiling the chemical fingerprint of phosphorus-rich stars: I. In the infrared region of APOGEE-2

The origin of phosphorus, one of the essential elements for life on Earth, is currently unknown. Prevalent models of Galactic chemical evolution (GCE) systematically underestimate the amount of P compared to observations, especially at low metallicities. The recently discovered P-rich ([P/Fe] ≳ 1.2 dex) and metal-poor ([Fe/H] ≃ –1.0 dex) giants further challenge the GCE models, calling current theories on stellar nucleosynthesis into question. Since the observed low-mass giants are not expected to produce their high P contents themselves, our primary goal is to find clues on their progenitor or polluter. By increasing the number of known P-rich stars, we aim to narrow down a statistically reliable chemical abundance pattern that defines these peculiar stars. In this way, we place more robust constraints on the nucleosynthetic mechanism that causes the unusually high P abundances. In the long term, identifying the progenitor of the P-rich stars may contribute to the search for the source of P in our Galaxy. We performed a detailed chemical abundance analysis based on the high-resolution near-infrared (H band) spectra from the latest data release (DR17) of the APOGEE-2 survey. Employing the BACCHUS code, we measured the abundances of 13 elements in the inspected sample, which is mainly composed of a recent collection of Si-enhanced giants. We also analyzed the orbital motions and compared the abundance results to possible nucleosynthetic formation scenarios, and also to detailed GCE models. These models were produced with the OMEGA+ chemical evolution code, using four different massive star yield sets to investigate different scenarios for massive star evolution. We enlarged the sample of confirmed P-rich stars from 16 to a group of 78 giants, which represents the largest sample of P-rich stars to date. The sample includes the first detection of a P-rich star in a Galactic globular cluster. Significant enhancements in O, Al, Si, and Ce, as well as systematic correlations among the studied elements, unveil the unique chemical fingerprint of the P-rich stars. In contrast, the high [Mg/Fe] and [(C+N)/Fe] found in some of the P-rich stars with respect to P-normal stars is not confirmed over the full sample because of the current uncertainties. Strikingly, the strong overabundance in the α-element Si is accompanied by normal Ca and S abundances. This is at odds with current stellar nucleosynthesis models of massive stars. Our analysis of the orbital motion showed that the P-rich stars do not belong to a locally specific population in the Galaxy. In addition, we confirm that the majority of the sample stars are not part of binary systems.

79 ASTRONOMY AND ASTROPHYSICS↗

Fastener load tests and retention systems tests for cryogenic wind-tunnel models

A-286 stainless steel screws were tested to determine the tensile load capability and failure mode of various screw sizes and types at both cryogenic and room temperature. Additionally, five fastener retention systems were tested by using A-286 screws with specimens made from the primary metallic alloys that are currently used for cryogenic models. The locking system effectiveness was examined by simple no-load cycling to cryogenic temperatures (-275 F) as well as by dynamic and static loading at cryogenic temperatures. In general, most systems were found to be effective retention devices. There are some differences between the various devices with respect to ease of application, cleanup, and reuse. Results of tests at -275 F imply that the cold temperatures act to improve screw retention. The improved retention is probably the result of differential thermal contraction and/or increased friction (thread-binding effects). The data provided are useful in selecting screw sizes, types, and locking devices for model systems to be tested in cryogenic wind tunnels.

Wallace, J. W.↗

Characterization of 3D printing filaments containing metal additives and their particulate emissions

Polylactic acid (PLA) filaments are widely used in fused filament fabrication (FFF) processes (3D printing). Filament additives such as metallic particles incorporated into PLA to modify functional and aesthetic features of print objects are becoming increasingly popular. However, the identities and concentrations of low percentage and trace metals in these filaments have not been well described in either the literature or product safety information included with the product. Here, we report the structures and concentrations of metals in selected Copperfill, Bronzefill and Steelfill filaments. We also report size-weighted number concentrations and size-weighted mass concentrations of particulate emissions as a function of print temperature for each filament. Particulate emissions were heterogenous in shape and size with airborne particles below 50 nm diameter dominating the size-weighted particle concentrations and larger particles (approximately 300 nm) dominating the mass weighted particle concentration. Results indicate that potential exposure to particles in the nano-size range increase when using print temperatures above 200o C. Because inhalation exposure to nanoparticles has been linked to adverse health outcomes, we suggest that using lower print temperatures for specific metal-fill filaments may reduce their operational hazard.

36 MATERIALS SCIENCE↗

The X-ray spectrum of Abell 665

The X-ray spectrum of the Abell 665 cluster of galaxies has been determined by the Ginga satellite. The spectrum can be well fitted by an isothermal model with kT = 8.26(+0.95; -0.81) keV and metal abundance 0.49 +/- 0.16. Joint analysis with lower energy spectral data from the Einstein Observatory is used to constrain the temperature distribution in the cluster. For a particular form of the polytropic temperature model we find the best fit to be the isothermal case, and we set an upper limit on the polytropic index of 1.35 (99-percent confidence). The virial mass of the cluster has been determined from both the X-ray data and the galaxy velocity dispersion. The mass estimates from the optical and X-ray analyses are fully consistent with each other. Abell 665 is found to be 0.82(+0.41; -0.26) times as massive as Coma if the two clusters are assumed to have the same spatial distribution of virial mass.

Hughes, John P.↗

Development of an On-board Failure Diagnostics and Prognostics System for Solid Rocket Booster

We develop a case breach model for the on-board fault diagnostics and prognostics system for subscale solid-rocket boosters (SRBs). The model development was motivated by recent ground firing tests, in which a deviation of measured time-traces from the predicted time-series was observed. A modified model takes into account the nozzle ablation, including the effect of roughness of the nozzle surface, the geometry of the fault, and erosion and burning of the walls of the hole in the metal case. The derived low-dimensional performance model (LDPM) of the fault can reproduce the observed time-series data very well. To verify the performance of the LDPM we build a FLUENT model of the case breach fault and demonstrate a good agreement between theoretical predictions based on the analytical solution of the model equations and the results of the FLUENT simulations. We then incorporate the derived LDPM into an inferential Bayesian framework and verify performance of the Bayesian algorithm for the diagnostics and prognostics of the case breach fault. It is shown that the obtained LDPM allows one to track parameters of the SRB during the flight in real time, to diagnose case breach fault, and to predict its values in the future. The application of the method to fault diagnostics and prognostics (FD&P) of other SRB faults modes is discussed.

Smelyanskiy, Vadim N.↗

Model for Humidity-Mediated Diffusion on Aluminum Surfaces and Its Role in Accelerating Atmospheric Aluminum Corrosion

Bare aluminum metal surfaces are highly reactive, which leads to the spontaneous formation of a protective oxide surface layer. Because many subsequent corrosive processes are mediated by water, the structure and dynamics of water at the oxide interface are anticipated to influence corrosion kinetics. Here, using molecular dynamics simulations with a reactive force field, we model the behavior of aqueous aluminum metal ions in water adsorbed onto aluminum oxide surfaces across a range of ion concentrations and water film thicknesses corresponding to increasing relative humidity. We find that the structure and diffusivity of both the water and the metal ions depend strongly on the humidity of the environment and the relative height within the adsorbed water film. Aqueous aluminum ion diffusion rates in water films corresponding to a typical indoor relative humidity of 30% are found to be more than 2 orders of magnitude slower than self-diffusion of water in the bulk limit. Connections between metal ion diffusivity and corrosion reaction kinetics are assessed parametrically with a reductionist model based on a 1D continuum reaction–diffusion equation. Our results highlight the importance of incorporating the properties specific to interfacial water in predictive models of aluminum corrosion.

36 MATERIALS SCIENCE↗

Bidentate N‐based Ligands for Highly Reusable, Ligand‐coordinated, Supported Pt Hydrosilylation Catalysts

Abstract A significant challenge in designing supported metal‐ligand catalysts for solution‐phase reactions is the stabilization of the metal active sites against leaching into solution. Here, we examine alkene hydrosilylation reactions as model systems to improve the stability of highly dispersed Pt using a metal‐ligand coordination strategy on high surface area oxide supports. By evaluating a series of bidentate N‐based ligands, we demonstrate several design strategies to improve stability of the highly dispersed Pt 2+ centers against leaching, while maintaining a high level of catalytic activity, selectivity, and recyclability for alkene hydrosilylation batch reactions under mild conditions. These involve a bi‐functional approach to ligand design, which considers interaction to the support and a well‐defined coordination environment for the metal active site. Three strategies are reported: modifying ligands for stronger interaction with oxide surfaces, mixing ligands, and pre‐depositing an “anchoring ligand” to the support before loading the metal‐ligand catalyst. Each of these is successful in enhancing Pt recyclability. Particularly, two Pt‐phenanthroline catalysts exhibit excellent reusability for multiple batch reaction cycles, due to high stability of the active Pt species. Addressing the active site leaching problem significantly enhances the utility of ligand‐coordinated supported metal catalysts as highly stable and selective catalysts for solution‐phase reactions.

Chen, Linxiao↗

Observation of Transition from Rate Law to Butler–Volmer Controlled Water Oxidation Kinetics on Hematite Photoanodes

Despite its central role in photoelectrochemical (PEC) water splitting, the mechanistic pathway of water oxidation on metal oxides remains unresolved, with population-based and Butler–Volmer (BV) models offering distinct views on how surface valence band holes drive the reaction. Here, we bring together these two perspectives by combining operando photoinduced absorption (PIA) spectroscopy with photocurrent analyses on α-Fe 2 O 3 (hematite) photoanodes as a function of light intensity. We find a crossover from population-controlled, rate law water oxidation at low hole densities to a BV-like, potential driven regime at high densities, triggered by band edge unpinning once surface M–OH species are fully oxidized, and excess holes accumulate without compensation. This mechanistic transition unifies competing models of interfacial charge transfer and reveals design principles for optimizing water oxidation in metal oxide photoelectrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advances in Studies of Electrode Kinetics and Mass Transport in AMTEC Cells

Previous work reported from JPL has included characterization of electrode kinetics and alkali atom transport from electrodes including Mo, W, WRh x (Mn), in sodium AMTEC cells and vapor exposure cells; and Mo in potassium vapor exposure cells. These studies were generally performed in cells with small area electrodes (about 1 to 5 cm 2 ), and device geometry had little effect on transport. Alkali metal diffusion coefficients through these electrodes have been characterized, and approximate surface diffusion coefficients were derived in cases of activated transport. A basic model of electrode kinetics and transport at the alkali metal vapor/pourous metal electrode/alkali beta"-alumina solid electrolyte (BASE) three phase boundary has been proposed which accounts for electrochemical reaction rates with a collision frequency near the three phase boundary and tunneling from the porous electrode partially covered with adsorbed alkali metal atoms. The small electrode effect in AMTEC cells has been discussed in several papers, but quantitative investigations have described only the overall effect and the important contribution of electrolyte resistance. The quantitative characterization of transport losses in cells with large area electrodes has been limited to simulations of large area electrode effects, or characterization of transport losses from large area electrodes with significant longitudinal temperature gradients. This paper describes new investigations of electrochemical kinetics and transport, with four 14.4 cm 2 WPt 3.5 electrodes, including the influence of electrode size on the mass transport loss in the AMTEC cell. These electrodes exhibit very slow sintering, as well as excellent sodium transport properties, making them attractive candidates for AMTEC power conversion use. However, the facile sodium transport in WPt 3.5 electrodes makes characterization of the transport process difficult.

electrode↗

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile element abundances in the Martian mantle and a mass balance constraint from Fe, the experiments allow a determination of the mass of the Martian core (approx. 17 to 22 wt% of the planet) and its S content (approx.0.4 wt%). These modeling results indicate that Mars is depleted in S, and that its core is solid.

Gaetani, Glenn A.↗

Variable stars in Local Group galaxies – V. The fast and early evolution of the low-mass Eridanus II dSph galaxy

ABSTRACT We present a detailed study of the variable star population of Eridanus II (Eri II), an ultra-faint dwarf galaxy that lies close to the Milky Way virial radius. We analyse multi-epoch g, r, i ground-based data from Goodman and the Dark Energy Camera, plus F475W, F606W, F814W space data from the Advanced Camera for Surveys. We report the detection of 67 RR Lyrae (RRL) stars and 2 Anomalous Cepheids, most of them new discoveries. With the RRL stars, we measure the distance modulus of Eri II, μ0 = 22.84 ± 0.05 mag (D⊙ = 370 ± 9 kpc), and derive a metallicity spread of 0.3 dex (0.2 dex intrinsic). The colour distribution of the horizontal branch (HB) and the period distribution of the RRL stars can be nicely reproduced by a combination of two stellar models of [Fe/H] = (−2.62, −2.14). The overall low metallicity is consistent with the red giant branch bump location, 0.65 mag brighter than the HB. These results are in agreement with previous spectroscopic studies. The more metal-rich RRL and the RRab stars have greater central concentration than the more metal-poor RRL and the RRc stars that are mainly located outside ∼1 rh. This is similar to what is found in larger dwarf galaxies such as Sculptor, and in agreement with an outside-in galaxy formation scenario. This is remarkable in such a faint dwarf galaxy with an apparently single and extremely short (<1 Gyr) star formation burst. Finally, we have derived new and independent structural parameters for Eri II and its star cluster using our new data that are in very good agreement with previous estimates.

79 ASTRONOMY AND ASTROPHYSICS↗