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67 records · Page 4

Systematic determination of a material’s magnetic ground state from first principles

Abstract We present a self-consistent method based on first-principles calculations to determine the magnetic ground state of materials, regardless of their dimensionality. Our methodology is founded on satisfying the stability conditions derived from the linear spin wave theory (LSWT) by optimizing the magnetic structure iteratively. We demonstrate the effectiveness of our method by successfully predicting the experimental magnetic structures of NiO, FePS 3 , FeP, MnF 2 , FeCl 2 , and CuO. In each case, we compared our results with available experimental data and existing theoretical calculations reported in the literature. Finally, we discuss the validity of the method and the possible extensions.

Chemistry↗

Grain boundary widening controls siderite (FeCO3) replacement of limestone (CaCO3)

Abstract The microstructure of minerals and rocks can significantly alter reaction rates. This study focuses on identifying transport paths in low porosity rocks based on the hypothesis that grain boundary widening accelerates reactions in which one mineral is replaced by another (replacement reaction). We conducted a time series of replacement experiments of three limestones (CaCO 3 ) of different microstructures and solid impurity contents using FeCl 2 . Reacted solids were analyzed using chemical imaging, small angle X-ray and neutron scattering and Raman spectroscopy. In high porosity limestones replacement is reaction controlled and complete replacement was observed within 2 days. In low porosity limestones that contain 1–2% dolomite impurities and are dominated by grain boundaries, a reaction rim was observed whose width did not change with reaction time. Siderite (FeCO 3 ) nucleation was observed in all parts of the rock cores indicating the percolation of the solution throughout the complete core. Dolomite impurities were identified to act as nucleation sites leading to growth of crystals that exert force on the CaCO 3 grains. Widening of grain boundaries beyond what is expected based on dissolution and thermal grain expansion was observed in the low porosity marble containing dolomite impurities. This leads to a self-perpetuating cycle of grain boundary widening and reaction acceleration instead of reaction front propagation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of cellulose to high-yield glucose in water over sulfonated mesoporous carbon fibers with optimized acidity

The hydrolysis of cellulose to high-yield glucose in water remains challenging owing to the limited acidity and substrate contact of sulfonated carbons. In this study, we report a unique sulfonated mesoporous carbon fiber with optimized acidity prepared by the pyrolysis of FeCl 3 -impregnated wipe fibers followed by acid treatment. The Bronsted acidity (especially for SO 3 H) was produced by sulfonation of the magnetic carbon fiber intermediate, while Lewis acidity originated from small Fe 3 O 4 nanoparticles and the remaining defects. The balanced Bronsted and Lewis acidity combined with hydrophilic functionalities was simultaneously tailored by varying the Fe/wipe fiber (WF) feed ratio and pyrolysis temperature to change the porous structure of the final catalysts. The elaborately fabricated MCF-SO 3 H-20-500 (20% Fe/WF feed ratio and pyrolysis at 500 degrees C) delivered 66.0% glucose yield as cellulose was completely converted. This is the highest glucose yield achieved by the hydrolysis of untreated cellulose in water over a sulfonated carbon catalyst. The optimized Bronsted and Lewis acidity was mainly responsible for the controlled conversion of cellulose to glucose, while the rich hydrophilic functionalities and superior mesoporous structure of the catalyst facilitated contact to cellulose and mass transfer. This investigation will open new avenues to design high-performance carbon sulfoacid catalysts toward cellulose hydrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relativistic nonorthogonal configuration interaction: application to L 2,3 -edge X-ray spectroscopy

In this article, we develop a relativistic exact-two-component nonorthogonal configuration interaction (X2C-NOCI) for computing L-edge X-ray spectra. This article to our knowledge is the first time NOCI has been used for relativistic wave functions. A set of molecular complexes, including SF 6 , SiCl 4 and [FeCl 6 ] 3– , are used to demonstrate the accuracy and computational scaling of the X2C-NOCI method. Here, our results suggest that X2C-NOCI is able to satisfactorily capture the main features of the L 2,3 -edge X-ray absorption spectra. Excitations from the core require a large amount of orbital relaxation to yield reasonable energies and X2C-NOCI allows us to treat orbital optimization explicitly. However, the cost of computing the nonorthogonal coupling is higher than in conventional CI. Here, we propose an improved integral screening using overlap-scaled density combined with a continuous measure of the generalized Slater–Condon rules that allows us to estimate if an element is zero before attempting a two-electron integral contraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

C sp 2 –H/F bond activation and borylation with iron

Reduction of [K 2 {( tBu pyrr 2 pyr)Fe} 2 (μ-N 2 )] (1) with two equiv. of KC 8 in the presence of crown-ether 18-C-6 yields the N 2 adduct [{K(18-C-6)} 2 ( tBu pyrr 2 pyr)Fe(N 2 )] (2). Complex 2 heterolytically splits the C sp 2 –H bond of benzene to form [{K(18-C-6)}( tBu pyrr 2 pyr)Fe(C 6 H 5 )] (3), whereby usage of a diboron B 2 pin 2 promotes hydride elimination to form the salt [K(18-C-6)HB 2 Pin 2 ] (4). Similarly, 3 can also be formed by cleavage of the C–F bond of fluorobenzene. Reaction of 3 with ClBcat yields [K(18-C-6)(thf) 2 ][( tBu pyrr 2 pyr)FeCl] (5) and PhBcat and the former can be reduced to 2 to complete a synthetic cycle for heterolytic benzene C–H activation and borylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability and magnetic behavior of exfoliable nanowire one-dimensional materials

Low-dimensional materials can display enhanced electronic, magnetic, and quantum properties. Here we use the topological scaling algorithm to identify all sufficiently metastable materials in the Materials Project database to identify bulk crystals with one-dimensional (1D) structural motifs: Five hundred fifty-one crystals that are within 50 meV atom –1 of the thermodynamic hull display 1D motifs, where 293 of these contain d-valence elements, which we focus on in this work. After exfoliating nanowires from 263 of these materials and calculating their thermodynamic stability using density functional theory, 103 nanowires meet per-atom and per-Ångström thermodynamic stability criteria. We illustrate for three nanowire systems that a variety of local minima can be present in these systems, demonstrating one case of a Peierls distortion. The wires display a broad diversity of electronic and magnetic properties of these nanowires, with 14 metals, 7 half-metals, and 82 semiconductors and insulators, and 41 nanowires displaying magnetic moments ranging from 0.1 to 5μ B per d-valence species when assuming ferromagnetic order. A subset of these chains are investigated for the impact of magnetic ordering, identifying 1D FeCl 3 to be most stable in an antiferromagnetic state. The electronic and magnetic properties of the identified 1D materials could enable applications in spintronic and quantum devices.

36 MATERIALS SCIENCE↗

Choline Chloride-Based Water-in-Salt Electrolyte for Efficient Iron Electrodeposition

Electrochemical production of iron is a promising low-cost and modular approach to replace the traditional blast furnace. Aqueous electrolytes for iron electrolysis are advantageous as they can be operated at near-ambient temperatures, but they suffer from inefficiencies due to the parasitic hydrogen evolution reaction. In this work, we identify a new water-in-salt electrolyte (WiSE) based on choline chloride (ChCl) for high coulombic efficiency (>85%) iron deposition. Electrochemical analysis of the partial current densities of iron plating and hydrogen co-evolution revealed that, at optimal WiSE compositions, water reduction is kinetically suppressed resulting in an increase in the Fe plating efficiency. Decreased coordination of water and increased coordination of choline’s alcohol group with the Fe 2+ ion were observed through 1 H NMR providing evidence that water reduction is kinetically suppressed in WiSE. Additionally, Raman spectroscopy revealed that complexation effects (with Cl – ) reduce Fe 2+ diffusion coefficients and corresponding limiting currents as the ChCl concentration is increased. This results in an optimal WiSE composition (4 M ChCl + 1 M FeCl 2 ) that provides kinetic suppression of HER but also low transport resistance to Fe plating yielding 85% coulombic efficiency at high current densities.

Sinclair, Nicholas Scott [Case Western Reserve Uni↗

Effect of Soluble Corrosion Products on Electrical Double Layer in LiCl-KCl Molten Salts

Corrosion in molten salts greatly hampers the application for renewable energy applications like molten salt reactors. To develop effective strategies for corrosion mitigation, understanding the interfacial structures and properties such as specific ion adsorption and electrical double layer capacitance are crucial. Using cyclic voltammetry and electrochemical impedance spectroscopy, we systematically studied the interfaces on various model electrodes including W (solid), Bi (liquid), and the stainless steel 316 in LiCl-KCl eutectic molten salts with the addition of corrosion species CrCl 2 and FeCl 2 . Both Cr 2+ and Fe 2+ ions increased electrical double layer capacitance, with Cr 2+ showing specific adsorption behavior and shifting the potential of zero charge, while Fe 2+ had minimal effect on point of zero charge. Two-working electrode measurements revealed increasing open-circuit potential and electrical double layer capacitance during the exposure of stainless steel 316, indicating its progressive corrosion and ion accumulation at the interface. X-ray photoelectron spectroscopy and Raman confirmed Cr enrichment at the interface. This work highlights the strong correlation between electrical double layer behavior and corrosion dynamics in molten salts and suggests electrical double layer capacitance as a sensitive, in situ indicator for corrosion monitoring.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Highly Catalytically Active High-spin Single-atom Iron Catalyst Supported by Catechol-containing Microporous 2D Polymer

Traditionally, Fe-SACs are prepared through energy-intense processes, which often lead to the loss of precision in structural features from the starting substrates and impeding rational design. In this work, we have described the synthesis of a unique catechol-containing porous polymer with designed features in the substrates maintained, affording atomically dispersed iron catalyst (Fe-SAC) through treatment of ferrous chloride (FeCl 2 ). An aberration-corrected scanning transmission electron microscope (AC-STEM) and synchrotron X-ray absorption spectroscopy (XAS) were employed to shed light on the local coordination geometry of the atomically dispersed iron catalyst. The resulting Fe-SAC exhibits excellent catalytic performance in reduction of nitroaromatics with highest molar K app among all Fe based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exopolysaccharide is required for motility, stress tolerance, and plant colonization by the endophytic bacterium Paraburkholderia phytofirmans PsJN

Paraburkholderia phytofirmans PsJN is an endophytic bacterium and has been shown to promote the growth and health of many different plants. Exopolysaccharide (EPS) plays important roles in plant-bacteria interaction and tolerance to environmental stresses. However, the function of EPS in PsJN and its interaction with plants remain largely unknown. In this study, a deletion mutation of bceQ gene, encoding a putative flippase for the EPS biosynthesis, was introduced in the genome of PsJN. The ΔbceQ mutant produced a significantly lower level of EPS than the wild type strain in culture media. Compared to the wild type PsJN, the ΔbceQ mutant was more sensitive to desiccation, UV damage, salt (NaCl) and iron (FeCl 3 ) stresses, and bacteriophage infection. More importantly, the mutation of bceQ decreased the endophytic colonization of PsJN in camelina (Camelina sativa) and pea (Camelina sativa) under plant drought stress conditions. To the best of our knowledge, this is the first report that EPS production is required for the maximal colonization of an endophytic bacterium in the plant tissues under stress conditions.

59 BASIC BIOLOGICAL SCIENCES↗

VERNE: Revealing the Mysteries and Histories of Venus

Introduction: The three Venus missions that were recently selected for upcoming flight (VERITAS, DAVINCI+, and EnVision) will be incredibly valuable to our understanding of Venus’ history, geology, and atmosphere. However, even once completed, key gaps in our knowledge of Venus, and more generally the formation and active processes on rocky, Earth-like planets, will still persist. Remaining questions include 1) how global intrinsic magnetic fields might be maintained on rocky worlds, and how they could then go extinct, and 2) what role atmospheric sulfur chemistry plays in climates of Earth-like planets, which is an increasingly timely subject as Earth’s own atmospheric sulfur content is climbing due to human activity. These questions require in-situ observations from Venus’ cloud deck, at the altitudes at which the UV absorber exists. The Venus Environment Research and Novel Exploration (VERNE) mission will address these questions with an aerial platform that will drift around the equatorial region of the planet for 9 days. VERNE will collect data to determine the identity of the mysterious UV absorber, while also taking magnetic field measurements over the tesserae, the regions on Venus that are most likely to retain remanent crustal magnetization, in order to understand the potential role of a past intrinsically-generated global magnetic field on Venus. Mission Objectives: The two major science objectives that drive the VERNE mission are: 1) Determine the identity of the Venusian unknown ultraviolet absorber(s). First observed approximately a century ago [1], the composition of Venus’ ultraviolet (UV) absorber is one of the oldest mysteries in Venus atmospheric chemistry [2,3]. While several candidate UV absorbers (mostly sulfur species) have been proposed, no consensus has been reached on its composition and its specific interactions with the atmosphere. Determining the identity of the UV absorber will aid climate models by showing how and where incident solar energy is absorbed by the atmosphere and make progress towards understanding the chemical and energetic processes taking place above Venus’ upper cloud deck [4]. 2) Determine if Venus retains evidence of a past, internally-generated magnetic field. While Venus does not currently have an intrinsically-generated magnetic field, evidence for the existence of a past field on Venus and a timeline of its decay will fill in a more holistic picture of the evolution of Venus’ geological record and atmosphere. As the oldest geologic units on the surface, Venus’ tesserae may still have remanent crustal magnetization signatures within the rocky composition [5]. In any case, the signatures detected will provide insight into Venus’ past geological and core dynamo activity. Mission Summary: VERNE includes a 3-part flight system made up of 1) an entry system with a HEEET (Heatshield for Extreme Entry Environment Technology) aeroshell, 2) an orbiter for data relay, and 3) an in-situ balloon and gondola. After entry into Venus’ atmosphere, the balloon will be deployed within the upper cloud deck, at an altitude of 62 km, over a tesserae region. The in-situ data collection will last for the duration of 2 full circumnavigations of the planet, which will take ~9 days. Instrumentation Suite: The four instruments that comprise VERNE’s instrument payload will enable the identification of the unknown UV absorber and the detection of remanent crustal magnetization if it exists in the tesserae. The proposed instrument suite cycle during mission operations is shown in Fig. 1. The four instruments are described below: 1) Adams (ion neutral mass spectrometer) has a range of 18-257 AMU and will detect and distinguish the mixing ratios of O₂, H₂O, H₂SO₄, S, S₂, S₃, S₄, S₅, S₆, S₇, S₈, SO, SO₂, OSSO, SO₃, Cl₂, FeCl₃ and other trace sulfur and organic species. The spatial (longitudinal) and temporal (day/night) variations will be observed throughout 2 circumnavigations with a sample cadence of 12 minutes. 2) Shelley (nephelometer) will determine the size distribution of the aerosols (0.4 to 36 um) in the atmosphere. With a size resolution of <0.7 um, it can determine which mode of H2SO4 is present and characterize the large (>30 um) organic particles previously detected by the Venera and Galileo missions [6,7]. 3) Herbert (UV imager) will measure UV radiance at 283 nm (the wavelength of SO2 absorption) and 365 nm (the unknown part of the absorber). UV images will be taken concurrently with the INMS and nephelometer to correlate UV absorption with abundances of the UV absorber species. 4) Vonnegut (magnetometer) has a range of >600 nT and a precision and accuracy of 1 nT. If magnetized by a past field, the crust may have retained a magnetization of up to 3 A/m2 [5]. With a noise floor of 10 nT, the magnetometer will be able to detect RCM from an altitude of 62 km, even if the thickness of the magnetized crust is just 1 km (Fig. 2). Mission Concept Design: VERNE will be launched with a mass of 3300 kg in an intermediate-high performance class vehicle with a 4-m fairing. The 475-day mission includes 466 days for the cruise, coasting, and orbit initialization phases before entry, descent, and balloon deployment. During the 9-day science phase, the aerial platform will make 2 circumnavigations of the planet at an altitude of 62 km. The INMS and the nephelometer will acquire data for 2 hours during the daytime and nighttime during each circumnavigation, while the UV imager will be on for the duration of the daytime, and the magnetometer will be operational throughout the entirety of the science phase. Data will be stored and processed with the JPL-designed Sphinx command and data handling system. Data will be sent from the balloon to the orbiter using an S-band relay link, stored on the orbiter, and then forwarded to Earth where it will be received by the DSN. Conclusion: VERNE will fill key gaps in our understanding of the history and ongoing processes related to the geology and atmosphere of Venus and rocky worlds in general. Even with adequate flight system contingencies and expected costs below the $900M New Frontiers cost cap, VERNE is not without its risks and challenges. Further trade spaces to explore include 1) using solely battery power vs. including solar panels to increase the mission duration and 2) investigating the use of lightweight materials and 3D-printed structures to reduce the gondola mass, among others. Acknowledgments: We would like to thank the JPL Planetary Science Summer School, especially our mentors Troy Hudson, Karl Mitchell, and Leslie Lowes, as well as our Team-X study lead Al Nash and the members of Team-X. We’d additionally like to thank our review panel for asking insightful questions and providing valuable feedback. References: [1] Ross, F. E. (1928) Astrophysical J., 68, 57-92. [2] Rossow, W. B. et al. (1980) J. Geophysical Research, 85, 8107-8128. [3] Pinto, J. P. et al. (2021) Nature Communications, 12, 175. [4] Titov, D. V. et al. (2007) Cosmic Research, 21, 401. [5] O’Rourke, J. et al. (2019) Geophysical Research Lett., 46, 5768–5777. [6] Limaye, S. S. et al. (2018) Astrobiology, 18(9), 1181-1198. [7] Grinspoon, D. H. et al. (2013) Planetary and Space Sci., 41(7), 515-542. [8] Parker, R. L. (2003) J. Geophysical Research, 108, 5006. *The cost information contained in this document is of a budgetary and planning nature and is intended for informational purposes only. It does not constitute a commitment on the part of JPL and/or Caltech.

H Alpert↗

Intermediate Temperature Ceramic Heat Pipe Modeling and Optimization

The intermediate temperature regime of heat pipes, 450-700 K, has not been well characterized due in part to the corrosive nature of many of the working fluids, as well as the poor performance in many conventional metal envelope systems. Spacecraft nuclear electric propulsion, as well as other emerging technologies, can benefit from heat pipes with optimal performance in this intermediate regime. In this work, we have explored halide working fluids coupled with aluminum nitride shells to operate at 500-600 K and interface with a nuclear electric propulsion system. The shells have been additively manufactured and tested to ensure compatibility with the halides. Specifically, AlBr 3 , AlCl 3 , FeCl 3 , and SbBr 3 were selected owing to their higher performance and comparatively safe handling characteristics compared to other intermediate temperature working fluids. The additive manufacturing process enables highly customizable designs that integrate the heat pipe and radiator fin together, optimized for each fluid. We have evaluated the performance limits of such a heat pipe design in order to establish the feasibility of AlBr 3 in particular, and present design that achieves an areal density of 5.2 kg/m 2 and mass per unit heat performance of 0.71 kg/kW. Analysis is ongoing for all working fluids.

thermal management↗