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Effect of Mg Content in Melt-Spun Mn–Bi–Mg–Sb–In Alloys on the Structure and Properties of Field-Annealed Magnets

Mn-Bi alloys modified with Mg and other elements were recently developed into promising rare-earth-free permanent magnets through successive melt-spinning, warm compaction, and short magnetic-field annealing. This letter reports herein on the crystal structures, texture, and magnetic properties observed in Mn 50 Bi 49-x Mg x Sb 0.5 In 0.5 alloys (x = 0, 1.5, 3.0, 4.5) throughout these processing steps. The Mg substitution favors MnBi-based intermetallic phases over the Bi- and Mn-based solid solutions and the stable α intermetallic phase over the metastable β' intermetallic phase. Magnesium increases the c/a ratio of the α phase lattice parameters for all studied x values and it increases the degree of the field-annealing-induced texture for x ≤ 3. The effect of Mg on coercivity is explained as combination of a positive one via the α phase magnetocrystalline anisotropy and a negative one via the development of texture. The effect of the substitution on the maximum energy product additionally involves the decreasing density of the alloys; the optimum x is found to be ≈3. Additionally reported are the thermal properties of selected alloys. The mechanism of field-annealing effect on the coercivity is briefly discussed.

36 MATERIALS SCIENCE↗

Nonlinear X-ray Optics

Novel X-ray free-electron lasers (XFELs) are capable of producing radiation with unprecedented properties. Specifically, their ultrashort coherent X-ray pulses can generate extreme peak intensities where ordinary rules of light-matter interaction may no longer apply, and nonlinear processes start to become important. XFELs have made it possible to observe some of the most important coherent non-sequential nonlinearities, including X-ray-optical sum frequency generation (SFG), X-ray second harmonic generation (XSHG), two-photon absorption (TPA) and nonlinear two-photon Compton scattering (2PCS). In particular, the 2PCS experiment has led to unexpected results, namely the observation of a substantial anomalous red shift in the energy of photons generated by nonlinear two-photon X-ray Compton scattering in beryllium. The energy shift is in addition to the predicted nonlinear Compton shift and was neither expected from extrapolations from linear X-ray interactions nor from nonlinear effects at optical wavelengths. Our results suggest a novel nonlinear scattering mechanism that can only be observed at high fields at X-ray wavelengths, where the photon energy is a significant fraction of the electron rest mass (and thus a significant momentum transfer to the electron occurs during the scattering) and where the interaction is not dominated by the quiver motion of the electron in the field (ponderomotive potential) as is usually the case at longer (optical) wavelengths. The goal of this research project was the investigation of fundamental nonlinear X-ray-matter interactions. As these processes are typically weak, part of this research is the exploration of more efficient nonlinear X-ray processes by studying novel mechanisms including solid-state effects, the assistance of optical radiation and novel phase-matching techniques. These experiments require extremely large X-ray field strengths, such as produced by XFELs. Nonlinear X-ray effects can lead to important applications in many research fields. For example, it could lead to instantaneous plasma diagnostics for materials in extreme conditions, as a method for combining atomic-scale structural sensitivity with chemical specificity, or as a probe of electron dynamics in solids on the attosecond (1 as = 10 -18 s) time- and Ångstrom (10 -10 m) length scales. In addition, a detailed understanding of nonlinear X-ray matter interactions is crucial for understanding and extending the limits of structural determination at high intensity such as in serial femto-crystallography. The results could have a profound impact on advanced XFEL light sources such as the LCLS-II.

47 OTHER INSTRUMENTATION↗

ISRU Technologies for Mars Life Support

Life support systems can take advantage of elements in the atmosphere of Mars to provide for necessary consumables such as oxygen and buffer gas for makeup of leakage. In situ consumables production (ISCP) can be performed effectively in conjunction with in situ propellant production, in which oxygen and methane are manufactured for rocket fuel. This project considers ways of achieving the optimal system objectives from the two sometimes competing objectives of ISPP and ISCP. In previous years we worked on production of a nitrogen-argon buffer gas as a by- product of the CO2 acquisition and compression system. Recently we have been focusing on combined electrolysis of water vapor and carbon dioxide. Combined electrolysis of water vapor and carbon dioxide is essential for reducin,o the complexity of a combined ISPP/ISCP plant. Using a solid oxide electrolysis cell (SOEC) for this combined process would be most advantageous for it allows mainly gas phase reactions, O2 gas delivered from the electrolyzer is free of any H2O vapor, and SOE is already a proven technology for pure CO2 electrolysis. Combined SOEC testing is conducted at The University of Arizona in the Space Technologies Laboratory (STL) of the Aerospace and Mechanical Engineering Department.

Finn, John E.↗

Method of producing superplastic alloys and superplastic alloys produced by the method

A method for producing new superplastic alloys by inducing in an alloy the formation of precipitates having a sufficient size and homogeneous distribution that a sufficiently refined grain structure to produce superplasticity is obtained after subsequent PSN processing. An age-hardenable alloy having at least one dispersoid phase is selected for processing. The alloy is solution heat-treated and cooled to form a supersaturated solid solution. The alloy is plastically deformed sufficiently to form a high-energy defect structure useful for the subsequent heterogeneous nucleation of precipitates. The alloy is then aged, preferably by a multi-stage low and high temperature process, and precipitates are formed at the defect sites. The alloy then is subjected to a PSN process comprising plastically deforming the alloy to provide sufficient strain energy in the alloy to ensure recrystallization, and statically recrystallizing the alloy. A grain structure exhibiting new, fine, equiaxed and uniform grains is produced in the alloy. An exemplary 6xxx alloy of the type capable of being produced by the present invention, and which is useful for aerospace, automotive and other applications, is disclosed and claimed. The process is also suitable for processing any age-hardenable aluminum or other alloy.

Troeger, Lillianne P.↗

Low Temperature Formation of Carbonaceous Grains from Hydrocarbons and PAHs with the COSmIC Facility

Complex carbon molecules and ions are ubiquitous in space and form the building blocks of the carbonaceous components of cosmic dust grains, ultimately contributing to the formation of planets. We report experimental investigations of the low temperature chemical pathways leading to the formation of cosmic grain analogs from gas phase molecular precursors to better understand the evolution of cosmic carbon. The study of the formation of dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. Although dust plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of carbonaceous dust. The experiments were performed using the Cosmic Simulation Chamber (COSmIC) to generate and characterize solid grains formed from gas phase precursors under controlled conditions representative of astrophysical environments [1]. Using COSmIC, it is possible to investigate the evolution of cosmic carbon from the formation of neutral and ionized hydrocarbons and PAHs in the gas phase [2], to solid carbon grains [3, 4, 5]. This is achieved by using a pulsed slit discharge nozzle to produce an adiabatic jet expansion and cool down Ar-hydrocarbon and PAH gas mixtures to astrophysically relevant temperature before inducing chemistry by generating a plasma discharge in the stream of the expansion. This plasma induced chemistry results in the formation of complex molecules and solid particles, analogs of cosmic grains in situ in the plasma expansion (i.e., without wall effects) that are carried by the accelerated gas in the expansion, and collected on substrates placed a few centimeters downstream of the electrodes. The results of a preliminary solid phase ex-situ analysis of cosmic grain analogs produced from a series of gas mixtures including hydrocarbons such as CH4 and C2H2 [3] and PAHs [4, 5] found in circumstellar ejecta of late C stars will be discussed. SEM imaging was used to provide insight on the impact of the precursors on the morphology and growth structure of the grains produced [3]. Laser desorption mass spectrometry was used to identify the molecules making up the main structures within the condensed grains [4] while X-ray irradiation and X-ray photoemission spectroscopy were used to investigate the impact the impact of stellar X-rays on cosmic dust.

Carbonaceous Grains↗

High-Accuracy Simulations to Model Pyrometallurgical Processes in a Secondary Lead Reverberatory Furnace

The US manufacturing industry produces about 1.3 million tons of refined lead each year using secondary sources consisting mainly of lead batteries. ORNL is partnering with Gopher resource, the second largest lead recycling company in the United States, and GTI, to develop a high-fidelity CFD model of a directly fired, reverberatory-style, secondary lead furnace. These High Performance Computing (HPC) simulations are aimed to use first principles modeling for combustion and melting processes of the secondary lead feed while accounting for complex interphase interactions between the gas, solid charge (lead) material, slag, and metal phases. Through validation against operating plant data, this effort will enable significant improvements in design, operational parameters, and energy efficiency, thus improving productivity and refractory lifetime of secondary lead melting furnaces. Estimated savings/reduction of, at least, 1 trillion BTU, 1 million ton/year of greenhouse gas emissions, and $\$50$ million/year to the US lead industry can be expected. ORNL resources and expertise in high-performance computing and multicomponent, multiphase flows were utilized to realize this goal while advancing the understanding of the smelting and melting processes occurring within the furnace.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Aqueous Zr/Hf IV ‐Oxo Cluster Speciation and Separation

Abstract Many industrial separations of chemically‐similar elements are achieved by solvent extraction, exploiting differences in speciation and solubility across aqueous‐organic interfaces. We recently identified [OM 4 (OH) 6 (SCN) 12 ] 4− (OM 4 , M=Zr/Hf IV ) tetrahedral oxoclusters as the main species in industrial processes that produce nuclear‐grade Zr and Hf from crude ore. However, isostructural/isoelectronic OM 4 ‐oxoclusters do not explain selective extraction of Hf into the organic phase. Here we have characterized heterometal Hf−Zr clusters in solution and the solid‐state yielding key information about their fundamentally different chemistry that engenders separation. Clusters prepared with both ammonium (industrial process) and tetramethylammonium counter cations revealed that 1) heterometal clusters (instead of a mixture of homometal clusters) assemble, and 2) Hf‐rich OM 4 selectively precipitates over Zr‐rich OM 4 , providing a separation process that does not require an organic extractant. Mass spectrometry, small‐angle X‐ray scattering, solution‐state 1 H nuclear magnetic resonance (NMR) spectroscopy, and solid‐state 17 O NMR evidence both mixed‐metal speciation and selective Hf‐precipitation. Raman spectroscopy suggests greater Zr‐ligand lability than Hf‐ligand lability, consistent with higher aqueous solubility of Zr‐rich clusters, enabling both extraction and precipitation‐based separation. Fundamentally, we also identify a key difference between these chemically similar elements that has enabled diversification of Zr‐polyoxocation chemistry over the last decade, while Hf‐polyoxocation chemistry lags.

Roseborough, Alexander [Department of Chemistry Or↗

Immiscible phase incorporation during directional solidification of hypermonotectics

Solidification processes in immiscible samples were investigated by directly observing the events taking place at the solid-liquid interface during directional solidification. Visualization of these events was made possible through the use of a transparent metal analog system and a temperature gradient stage assembly fitted to an optical microscope. The immiscible transparent analog system utilized was the succinonitrile-glycerol system. This system has been shown to exhibit the same morphological transitions as observed in metallic alloys of monotectic composition. Both monotectic and hypermonotectic composition samples were directionally solidified in order to gain an improved understanding of the manner in which the excess hypermonotectic liquid is incorporated into the solidifying structure. The processing conditions utilized prevented sedimentation of the excess hypermonotectic liquid by directionally solidifying the samples in very thin (13 microns), horizontally oriented cells. High thermal gradient to growth rate ratios (G/R) were used in an effort to prevent constitutional supercooling and the subsequent formation of L(sub 2) droplets in advance of the solidification front during the growth of fibrous composite structures. Results demonstrated that hypermonotectic composites could be produced in samples up to two weight percent off of the monotectic composition by using a G/R ratio greater than or equal to 4.6 x 10(exp 4) C(s)/mm(sup 2) to avoid constitutional supercooling. For hypermonotectic samples processed with G/R ratios below 4.6 x 10(exp 4) C(s)/mm(sup 2), constitutional supercooling occurred and resulted in slight interfacial instability. For these samples, two methods of incorporation of the hypermonotectic liquid were observed and are reported. The correlation between the phase spacing, lambda, and the growth rate, R, was examined and was found to obey a relationship generally associated with a diffusion controlled coupled growth process. For samples with compositions ranging from the monotectic composition up to 2 percent off of the monotectic composition, data indicated that the square of the phase spacing (lambda) varied linearly with the inverse of the growth rate (R).

Andrews, J. Barry↗

Synthesis and Photonic Sintering of Proton Conducting Lanthanide Nickelates

Lanthanide nickelate perovskites are known proton conductors at intermediate temperatures (350-600°C). They are attractive targets for proton conducting fuel cells and electrolyzers due to their operational temperature range and their stability in the presence of CO 2 . These materials have the formula LNiO 3 , with the lanthanide L = La, Ce, Pr, Nd, or Sm. Sintering is challenging due to phase transformations that occur at lower temperatures than those required for sintering. In this project, a series of lanthanide nickelate perovskites was synthesized via both a precursor solid solution method and the glycine nitrate process. Powders derived from the precursor solid solution method for LaNiO 3 and NdNiO 3 were sintered at Utility Global Inc. at various temperatures utilizing fast photonic sintering. LaNiO 3 was successfully sintered while maintaining the perovskite phase. NdNiO 3 underwent a phase transformation at all the conditions tested. The stability of the perovskite phase decreases moving right across the lanthanides in the periodic table, while the expected proton conductivity increases. These results will inform further investigations into lanthanide nickelate perovskites toward the goal of producing a free-standing, sintered, proton-conducting membrane.

36 MATERIALS SCIENCE↗

Regulating electrodeposition morphology of lithium: towards commercially relevant secondary Li metal batteries

Lithium, the lightest and most electronegative metallic element, has long been considered the ultimate choice as a battery anode for mobile, as well as in some stationary applications. The high electronegativity of Li is, however, a double-edged sword—it facilitates a large operating voltage when paired with essentially any cathode, promising a high cell-level energy density. It is also synonymous with a high chemical reactivity and low reduction potential. The interfaces a Li metal anode forms with any other material (liquid or solid) in an electrochemical cell are therefore always mediated by one or more products of its chemical or electrochemical reactions with that material. The physical, crystallographic, mechanical, electrochemical, and transport properties of the resultant new material phases (interphases) regulate all interfacial processes at a Li metal anode, including electrodeposition during battery recharge. This Review takes recent efforts aimed at manipulating the structure, composition, and physical properties of the solid electrolyte interphase (SEI) formed on an Li anode as a point of departure to discuss the structural, electrokinetic, and electrochemical requirements for achieving high anode reversibility. An important conclusion is that while recent reports showing significant advances in the achievement of highly reversible Li anodes, e.g. as measured by the coulombic efficiency (CE), raise prospects for as significant progress towards commercially relevant Li metal batteries, the plateauing of achievable CE values to around 99 ± 0.5% apparent from a comprehensive analysis of the literature is problematic because CE values of at least 99.7%, and preferably >99.9% are required for Li metal cells to live up to the potential for higher energy density batteries offered by the Li metal anode. On this basis, we discuss promising approaches for creating purpose-built interphases on Li, as well as for fabricating advanced Li electrode architectures for regulating Li electrodeposition morphology and crystallinity. Considering the large number of physical and chemical factors involved in achieving fine control of Li electrodeposition, we believe that achievement of the remaining ~0.5% in anode reversibility will require fresh approaches, perhaps borrowed from other fields. We offer perspectives on both current and new strategies for achieving such Li anodes with the specific aim of engaging established contributors and newcomers to the field in the search for scalable solutions.

25 ENERGY STORAGE↗

Mineralogical Analysis of Calcium-Aluminum-Rich Inclusions Provides Insight Into Post-Formation Processes

Introduction: Calcium-aluminum inclusions (CAIs) are cm- to mm-sized intergrowths of refractory phases found in chondritic meteorites [1]. Their mineral compositions closely match the compositions of the solids thought to condense from an extremely hot (>1500K) gas with a bulk solar composition [2-4], suggesting that CAIs were the earliest solids within the Solar System [2-4]. These inclusions provide invaluable insights into the conditions and dynamics of the early Solar System. CAIs must be transported from their formation region near the protosun to the chondrite parent-body accretion region. The nature of their journey could affect how, when, and where the secondary processes recorded in these CAIs occurred [4]. Did these secondary processes occur in the solar nebula or during accretion with the parent body, or both? How were the CAIs affected by varying thermochemical processes? To better answer these questions, we have undertaken an in-depth, textural study of the secondary alteration of select CAI samples. Methods: We chose three CAIs that experienced a range of post-formation processing to gain better understanding of secondary alteration based on previous preliminary examination [5]. Representative CAIs were chosen from NWA 5508 (CV3), NWA 12772 (CV3), and Coolidge (CL4) carbonaceous chondrites. We used scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) techniques for detailed chemical, mineralogical, and textural analysis of the CAIs. Backscattered electron (BSE) images and X-ray elemental maps were taken of Coolidge and NWA 5508 using the Lunar and Planetary Institute (LPI) Phenom SEM. The JEOL 7900F SEM at NASA Johnson Space Center (JSC) was used to obtain energy dispersive spectroscopy (EDS) chemical maps of all samples. High resolution EBSD analysis identified the mineral phases and textures, providing key information on their nature. Based on the SEM and EBSD data, minerals of interest were selected for quantitative chemical electron probe micro-analysis (EPMA) using the JEOL JXA-8530F at NASA JSC. Results and Discussion: The EDS maps show that the NWA 5508 and NWA 12772 CAIs designated “Saguaro” and “Hoopoe” respectively [5] are enriched in calcium while the Coolidge CAI designated “Cottonwood” is aluminum and magnesium rich. Saguaro. A ~1.5cm diameter igneous Type B CAI with a rounded shape. The dominant phases are melilite, spinel, and Al-Ti pyroxene with minor anorthite. Spinel is subhedral and occurs in clusters. Some of these clusters have a circular geometry which encloses other minerals, known as a palisade structure [6] (Fig. 1). Some palisades form near perfect circles while others are more irregular in shape. Melilite in Saguaro ranges in size from coarse (>250m) to fine-grained (5-7m) and forms intergrown laths. A third of the melilite grains exhibit simple twinning about their <001> axis. The spinel palisades and twinned melilite in Saguaro suggest an igneous history, and the lack of secondary minerals suggests minimal aqueous alteration. At some point in time after the initial condensation of the minerals and formation of the inclusion, the sample was remelted and quickly solidified. The formation of the palisades is still heavily debated. One hypothesis is that the palisades are the rims of smaller CAIs that accreted early on, essentially acting as xenoliths within the larger CAIs [7]. Another hypothesis suggests an igneous origin for palisade structures [6-8] wherein the melt traps gas bubbles, and the spinel nucleates on the surface of this bubble. Based on the WDS spot analyses of 41 melilite grains using EPMA, the data suggest that the composition inside and outside the palisades is nearly identical. This finding indicates that these palisades are likely not exogenous but rather formed from melt-vapor reactions. Our results are consistent with studies by Simon and Grossman,1997 [6] and Zhang et al. (2019) [8]. Hoopoe. A ~0.5cm compact Type A CAI with an irregular shape. The dominant mineral phases are melilite, spinel, and hibonite with minor amounts of anorthite, augite, and perovskite. The melilite ranges in size from ~500 to 50µm. The larger melilite grains have simple twinning along the <001> axis like melilite in Saguaro. Melilite in Hoopoe exhibits crystal-plastic strain with misorientation dominantly about the <010> and <110> axes. Spinel shows subhedral to euhedral morphology and appears in clusters. Hibonite grains are similar to spinel in habit and size but show more plastic strain. The two minerals are often found together with one appearing to replace the other. Perovskite appears in fine grained recrystallized regions alongside fine augite and spinel. The abundant strain and deformation features in the melilite and hibonite suggest that Hoopoe experienced shock. This shock could have occurred in the nebula [9] or from an impact of another body on the parent body asteroid. The appearance of fine-grained (<10m) areas of augite, perovskite, and spinel in the dominantly coarse-grained inclusion suggest recrystallization, possibly due to the sudden increase in pressure and temperature. Cottonwood. This ~0.5cm CAI exhibits distinct mineralogy and textures suggesting a high degree of alteration. It is irregular in shape. The dominant mineral phases are spinel and anorthite with minor amounts of augite and rutile. The two main texture types can be seen in Fig. 2. The first type consists of coarse euhedral to subhedral spinel and anorthite. The second includes fine grained spinel, anorthite, rutile, and iron sulfides. Within these fine-grained regions, the anorthite grains are clustered into domains exhibiting the same crystallographic orientation. Rutile exclusively occurs with fine anorthite indicating a potential relationship between the two. Cottonwood has a clear and unbroken Wark-Lovering [10] rim (Fig. 2) on one side that consists of a sequence of spinel followed by anorthite and an outer layer of augite. The abundance of the fine-grained regions containing iron oxides and iron sulfides, secondary phases such as rutile, and oriented anorthite grains is evidence for recrystallization associated with a high degree of thermal metamorphism. The EPMA analyses on both coarse- and fine-grained spinel show that the fine spinel grains are more enriched in Cr (1-2 wt. %) than their coarse counterparts (0.1-0.5 wt. %). The data suggest thermal metamorphism drove chemical exchange of the previously refractory inclusion, introducing chromium and iron as well as sulfur, which is moderately volatile. Conclusions: The three CAIs analyzed record distinct secondary nebular and parent body processes. Saguaro melted in the nebula as seen by the twinned melilite and spinel palisades. Hoopoe experienced intense shock which deformed its melilite and recrystallized perovskite, augite, and spinel in fine-grained regions. Cottonwood shows evidence of recrystallization and chemical changes consistent with thermal metamorphism occurring after accretion into the parent-body.

V E Burnette↗

Synchrotron-based techniques for characterizing STCH water-splitting materials

Understanding the role of oxygen vacancy–induced atomic and electronic structural changes to complex metal oxides during water-splitting processes is paramount to advancing the field of solar thermochemical hydrogen production (STCH). The formulation and confirmation of a mechanism for these types of chemical reactions necessitate a multifaceted experimental approach, featuring advanced structural characterization methods. Synchrotron X-ray techniques are essential to the rapidly advancing field of STCH in part due to properties such as high brilliance, high coherence, and variable energy that provide sensitivity, resolution, and rapid data acquisition times required for the characterization of complex metal oxides during water-splitting cycles. X-ray diffraction (XRD) is commonly used for determining the structures and phase purity of new materials synthesized by solid-state techniques and monitoring the structural integrity of oxides during water-splitting processes (e.g., oxygen vacancy–induced lattice expansion). X-ray absorption spectroscopy (XAS) is an element-specific technique and is sensitive to local atomic and electronic changes encountered around metal coordination centers during redox. While in operando measurements are desirable, the experimental conditions required for such measurements (high temperatures, controlled oxygen partial pressures, and H 2 O) practically necessitate in situ measurements that do not meet all operating conditions or ex situ measurements. Here, we highlight the application of synchrotron X-ray scattering and spectroscopic techniques using both in situ and ex situ measurements, emphasizing the advantages and limitations of each method as they relate to water-splitting processes. The best practices are discussed for preparing quenched states of reduction and performing synchrotron measurements, which focus on XRD and XAS at soft (e.g., oxygen K-edge, transition metal L-edges, and lanthanide M-edges) and hard (e.g., transition metal K-edges and lanthanide L-edges) X-ray energies. The X-ray absorption spectra of these complex oxides are a convolution of multiple contributions with accurate interpretation being contingent on computational methods. The state-of-the-art methods are discussed that enable peak positions and intensities to be related to material electronic and structural properties. Through careful experimental design, these studies can elucidate complex structure–property relationships as they pertain to nonstoichiometric water splitting. A survey of modern approaches for the evaluation of water-splitting materials at synchrotron sources under various experimental conditions is provided, and available software for data analysis is discussed.

08 HYDROGEN↗

Optical vibrational spectroscopic signatures of ammonium diuranate process parameters

Ammonium diuranate (ADU) is commonly encountered in the nuclear fuel cycle; however, previous investigations have shown that ADU is a complex mixture of distinct compounds. Moreover, production parameters are known to heavily influence the composition of the resulting ADU. Here, we examine four samples of ADU prepared at Oak Ridge National Laboratory (ORNL), and one sample of ADU made at Pacific Northwest National Laboratory (PNNL), with the goal of further characterizing and elucidating the effect of processing parameters such as stir rate, strike direction, and temperature on material composition. Process parameters during ADU precipitation at ORNL and PNNL were well documented, and we relate process variables to optical vibrational spectroscopic signatures observed using Raman and infrared (IR) spectroscopy. In addition, powder X-ray diffraction (PXRD) reveals differences in the solid-phase composition of ADU precipitates, but we find that the primary phase is similar to the uranyl oxyhydroxyhydrate mineral metaschoepite. Despite the significant phase contributions of a metaschoepite-like phase, spectroscopic evidence of both nitrate and ammonium are observed for all samples. To gain a more holistic understanding of spectroscopic features of process parameters in ADU, principal component analysis (PCA) is employed and results in observable signatures that relate to the stir rate used during synthesis. These results provide further information about the process-dependence of ADU precipitate composition.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Fundamental Phenomena on Fuel Decomposition and Boundary-Layer Combustion Precesses with Applications to Hybrid Rocket Motors: Experimental Investigation - Part 1

This final report summarizes the major findings on the subject of 'Fundamental Phenomena on Fuel Decomposition and Boundary-Layer Combustion Processes with Applications to Hybrid Rocket Motors', performed from 1 April 1994 to 30 June 1996. Both experimental results from Task 1 and theoretical/numerical results from Task 2 are reported here in two parts. Part 1 covers the experimental work performed and describes the test facility setup, data reduction techniques employed, and results of the test firings, including effects of operating conditions and fuel additives on solid fuel regression rate and thermal profiles of the condensed phase. Part 2 concerns the theoretical/numerical work. It covers physical modeling of the combustion processes including gas/surface coupling, and radiation effect on regression rate. The numerical solution of the flowfield structure and condensed phase regression behavior are presented. Experimental data from the test firings were used for numerical model validation.

Kuo, Kenneth K.↗

Al2O3 Atomic Layer Deposition on Nanostructured γ-Mg(BH4)2 for H2 Storage

In the context of the growing hydrogen (H 2 ) economy, the demand for H 2 storage materials is high, and metal borohydrides are of particular interest. Magnesium borohydride, Mg(BH 4 ) 2 , has one of the highest hydrogen capacities of all known metal hydrides (14.9 wt % H) but suffers from high operating temperatures, slow kinetics for (de)hydrogenation, and the loss of capacity upon cycling. Strategies to address these challenges include nanoencapsulation and the use of chemical additives. This work is the first to utilize these two strategies simultaneously by using atomic layer deposition (ALD). For this new approach to modify borohydrides, we chose the well-studied Al 2 O 3 ALD process using trimethylaluminum and water. Although there has been limited use of aluminum-based additives for Mg(BH 4 ) 2 , we demonstrate that the low-temperature H 2 capacity was doubled, desorption kinetics were increased by a factor of 3, and 100 cycles of Al 2 O 3 suppressed the release of diborane compared to the uncoated Mg(BH4)2. We identified that the use of trimethylaluminum and water in the ALD process affected the decomposition pathway and that the Al 2 O 3 film growth is dominated by infiltration due to the high porosity of the ..gamma..-phase Mg(BH 4 ) 2 . From these results, the potential of ALD as a method to functionalize solid-state H 2 storage materials is inferred, and recommendations for future ALD processes are presented.

08 HYDROGEN↗

Integrated lunar materials manufacturing process

A manufacturing plant and process for production of oxygen on the moon uses lunar minerals as feed and a minimum of earth-imported, process materials. Lunar feed stocks are hydrogen-reducible minerals, ilmenite and lunar agglutinates occurring in numerous, explored locations mixed with other minerals in the pulverized surface layer of lunar soil known as regolith. Ilmenite (FeTiO.sub.3) and agglutinates contain ferrous (Fe.sup.+2) iron reducible by hydrogen to yield H.sub.2 O and metallic Fe at about 700.degree.-1,200.degree. C. The H.sub.2 O is electrolyzed in gas phase to yield H.sub.2 for recycle and O.sub.2 for storage and use. Hydrogen losses to lunar vacuum are minimized, with no net hydrogen (or any other earth-derived reagent) consumption except for small leaks. Feed minerals are surface-mined by front shovels and transported in trucks to the processing area. The machines are manned or robotic. Ilmenite and agglutinates occur mixed with silicate minerals which are not hydrogen-reducible at 700.degree.-1,200.degree. C. and consequently are separated and concentrated before feeding to the oxygen generation process. Solids rejected from the separation step and reduced solids from the oxygen process are returned to the mine area. The plant is powered by nuclear or solar power generators. Vapor-phase water electrolysis, a staged, countercurrent, fluidized bed reduction reactor and a radio-frequency-driven ceramic gas heater are used to improve thermal efficiency.

Gibson, Michael A.↗

3D Printing of Liquid Crystal Elastomer Foams for Enhanced Energy Dissipation Under Mechanical Insult

Polymer foams are an essential class of lightweight materials used to protect assets against mechanical insults, such as shock and vibration. Two features are important to enhance their energy absorption characteristics: the foam structure and the matrix phase mechanical behavior. This study investigates novel approaches to control both of these features to enhance the energy absorption capability of flexible lattice foams. First, we consider 3D printing via digital light processing (DLP) as a method to control the foam mesostructure across a suite of periodic unit cells. Second, we introduce an additional energy dissipation mechanism in the solid matrix phase material by 3D printing the lattice foams with polydomain liquid crystal elastomer (LCE), which undergo a mechanically induced phase transition under large strains. This phase transition is associated with LC mesogen rotation and alignment and provides a second mechanism for mechanical energy dissipation in addition to the viscoelastic relaxation of the polymer network. Here, we contrast the 3D printed LCE lattices with conventional, thermomechanically near-equivalent elastomer lattice foams to quantify the energy-absorbing enhancement the LCE matrix phase provides. Under cyclic quasi-static uniaxial compression conditions, the LCE lattices show dramatically enhanced energy dissipation in uniaxial compression compared to the non-LCE equivalent foams printed with a commercially available photocurable elastomer resin. The lattice geometry also plays a prominent role in determining the energy dissipation ratio between the LCE and non-LCE foams. We show that when increasing the lattice connectivity, the foam deformation transitions from bending-dominated to stretching-dominated deformations, which generates higher axial strains in the struts and higher energy dissipation in the lattice foam, as stretching allows greater mesogen rotation than bending. The LCE foams demonstrate superior energy absorption during the repeated dynamic loading during drop testing compared with the non-LCE equivalent foams, demonstrating the potential of LCEs to enhance physical protection systems against mechanical impact.

3D printing↗

Advancements in Spacecraft Brine Water Recovery: Development of a Radial Vaned Capillary Drying Tray

Technology improvements in the recovery of water from brine are critical to establishing closedloop water recovery systems, enabling long duration missions, and achieving a sustained human presence in space. A genre of 'in-place drying' brine water recovery concepts, collectively referred to herein as Brine Residual In-Containment (BRIC), are under development which aim to increase the overall robustness and reliability of the brine recovery process by performing drying inside the container used for final disposal of the solid residual waste. Implementation of in-place drying techniques have been demonstrated for applications where gravity is present and phase separation occurs naturally by buoyancy induced effects. In this work, a microgravity compatible analogue of the gravity-driven phase separation process is considered by exploiting capillarity in the form of surface wetting, surface tension, and container geometry. The proposed design consists of a series of planar radial vanes aligned about a central slotted core. Preliminary testing of the fundamental geometry in a reduced gravity environment has shown the device to spontaneously fill and saturate rapidly creating a free surface from which evaporation and phase separation can occur similar to a 1-g like 'cylindrical pool' of fluid. Mathematical modeling and analysis of the design suggest predictable rates of filling and stability of fluid containment as a function of relevant system dimensions, e.g., number of vanes, vane length, width, and thickness. A description of the proposed capillary design solution is presented along with preliminary results from testing, modeling and analysis of the system.

Callahan, Michael R.↗