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At least 757 records · Page 42

Advanced Processing of Rare Earth Elements and Critical Minerals from Acid Mine Drainage Feedstocks

Ongoing work by the project team identified a process for extracting rare earths and critical mineral (REE/CM) concentrates from acid mine drainage from coal mines, a major stream pollutant. The process removes harmful metals and separates REE/CM into economically attractive concentrates. This project explored the processing of those concentrates into individually separated, high purity metals, suitable for domestic manufacturers. The team brought unique experience in working with AMD-based feedstocks since the inception of USDOE’s coal-based REE/CM program in 2016. The project team has pioneered the recovery of rare earth/critical minerals (REE/CM) from acid mine drainage (AMD). This environmentally beneficial strategy will incentivize AMD treatment while recovering materials critical to the Nation’s defense and advanced manufacturing industries. In addition, the project will investigate the co-production of five high purity CMs from AMD, namely Co, Mn, Li, Cr, Ge. This team’s upstream and midstream recovery and processing technology has been demonstrated at the continuous, small scale pilot scale. In conjunction with the West Virginia Department of Environmental Protection, the team is constructing a full-scale, integrated, 500 gpm AMD treatment plant coupled with an REE/CM facility that will produce 21 tons REE/CM per year. Commissioning is scheduled for September 2021. This will provide feedstock for the team’s proprietary downstream processes that met the project objective: production of individually separated, high purity (ISHP) REE/CM oxides and their further processing to elemental metals (REM). To facilitate entry into the U.S. market, we have teamed up with companies that would use our products to strengthen their domestic supply chains and grow REE/CM based manufacturing in the U.S. They include Rockwell Automation, Rivian, Endress+Hauser, Inc., Northrop Grumman and Hela Novel Metals.

01 COAL, LIGNITE, AND PEAT↗

Atomic Oxygen Treatment as a Method of Recovering Smoke Damaged Paintings

A noncontact technique is described that uses atomic oxygen, generated under low pressure in the presence of nitrogen, to remove soot and charred varnish from the surface of a painting. The process, which involves surface oxidation, permits control of the amount of surface material removed. The effectiveness of the process was evaluated by reflectance measurements from selected areas made during the removal of soot from acrylic gesso, ink on paper, and varnished oil paint substrates. For the latter substrate, treatment also involved the removal of damaged varnish and paint binder from the surface.

Rutledge, Sharon K.↗

Thermochemical Interactions of Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced from lunar resources through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar mare and highlands regolith simulants at 1600C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD with an emphasis on elemental and microstructural analysis to assess reactivity and degradation of YSZ. Due to lunar regolith’s similar composition to calcium-magnesium-aluminosilicates (CMAS) and YSZ’s usage as a thermal barrier coating, these interactions can serve to inform YSZ/CMAS behavior by simulating cases of elevated CMAS/YSZ ratios and for higher than intended gas turbine temperatures.

Kevin Yu↗

Digital Light Processing (DLP): 3D printing of polymer-based graphene oxide nanocomposites—Efficient antimicrobial material for biomedical devices

Bacterial infections are one of the major causes of surgical implant inefficiency and failure. Herein, we present a Nanocomposite (NC) produced by the addition of Poly(N-vinyl carbazole)-Graphene Oxide dispersion (PVK-GO) as a nanofiller to a commercial photopolymer acrylate resin and 3D printed as coatings via the Digital Light Processing technique. Characterization and bioassay results against Escherichia coli and Staphylococcus aureus confirmed the elevated thermomechanical properties and efficient antibacterial activity of the printed NC-based coatings. In conclusion, the present study demonstrates the fabrication and optimization of a PVK-GO-based NC and its potential utilization as a 3D-printable material for biomedical applications.

2D materials↗

Dissolution zone model of the oxide structure in additively manufactured dispersion-strengthened alloys

The structural evolution of oxides in dispersion-strengthened superalloys during laser-powder bed fusion is considered in detail. Alloy chemistry and process parameter effects on oxide structure are assessed through a parameter study on the model alloy Ni-20Cr, doped with varying concentrations of Y 2 O 3 and Al. Small angle neutron scattering measurements of the dispersoid size distribution show the dispersoid size increases with higher laser power, slower scan speed, and increasing Y 2 O 3 and Al content. Complementary electron microscopy measurements reveal reactions between Y 2 O 3 and Al, even in nanoscale dispersoids, and the presence of micron-scale oxide slag inclusions in select specimens. A scaling analysis of mass and momentum transport within the melt pool, presented here, establishes that diffusional structural evolution mechanisms dominate for nanoscale dispersoids, while fluid forces and advection become significant for larger slag inclusions. These findings are developed into a theory of dispersoid structural evolution, integrating quantitative models of diffusional processes – dispersoid dissolution, nucleation, growth, coarsening – with a reduced order model of time-temperature trajectories of fluid parcels within the melt pool. Calculations of the dispersoid size in single-pass melting reveal a zone in the center of the melt track in which the oxide feedstock fully dissolves. Within this zone the final Y 2 O 3 size is independent of feedstock size and determined by nucleation and growth kinetics. If the dissolution zones of adjacent melt tracks overlap sufficiently with each other to dissolve large oxides, formed during printing or present in the powder feedstock, then the dispersoid structure throughout the build volume is homogeneous and matches that from a single pass within the dissolution zone. Gaps between adjacent dissolution zones result in oxide accumulation into larger slag inclusions. Predictions of final dispersoid size and slag formation using this dissolution zone model match the present experimental data and explain process-structure linkages speculated in the open literature.

36 MATERIALS SCIENCE↗

Development of Oxidation Resistant Coatings on GRCop-84 Substrates by Cold Spray Process

GRCop-84, a Cu-CR-Nb alloy, has been developed for rocket engine liner applications. For maximum life additional oxidation protection is required to prevent blanching. NiCrAlY was identified as a suitable coating, and efforts were initiated to develop suitable coating techniques. Cold spray is one technique under consideration. Efforts at ASB Industries to produce dense, adherent coatings are detailed. The work culminated in the production of samples for testing at NASA Glenn Research Center.

Karthikeyan, J.↗

Oxidation of Silicon Carbide with Atomic Oxygen through the Passive-to-Active Transition

The inelastic and reactive scattering dynamics of O( 3 P) atoms on a 6H-silicon carbide (SiC) surface were investigated as a function of temperature with a molecular beam-surface scattering technique that employed a rotatable mass spectrometer detector. One set of experiments used a pulsed hyperthermal beam that produced ~8 km s –1 O atoms, and another set of experiments used a continuous beam that contained O atoms with a nominal velocity of ~2 km s –1 . When exposed to the relatively low-flux, pulsed hyperthermal O-atom beam, a passive oxide layer on the SiC that formed at lower temperatures decomposed as the temperature increased above 1673 K. Instead of entering an active oxidation regime, a graphitic layer formed on the surface and largely protected the underlying SiC from incoming O atoms. Investigation of the oxide decomposition without O-atom bombardment revealed volatile Si and SiO products at the moment that the oxide decomposed, implying that Si sublimation occurs concurrently with oxide decomposition. In the experiment with the continuous (higher flux) O-atom beam, volatile SiO and CO products were observed after the passive oxide decomposed, indicating that active oxidation was reached. Finally, the results of this study provide evidence for the importance of Si sublimation within the active oxidation regime. Above the passive-to-active transition temperature, Si sublimation is an ongoing process, and continuous active oxidation will only occur if sufficient oxygen reacts with the surface to produce SiO more quickly than a graphitic layer can form. Thus, accurate models of SiC ablation by atomic oxygen must account for multiple competing mechanisms that depend on the surface temperature and incident O-atom flux.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermochemical Interactions Between Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600 C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is shown here to be a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar maria and highlands regolith simulants at 1600 C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD. A FactSage thermochemical model is created to compare with the experimental results. These combined analyses suggest that lunar maria regolith will degrade YSZ faster than lunar highlands regolith due to the lower viscosity of the maria regolith. The feasibility of long-term molten regolith containment with YSZ is discussed based on the YSZ powder and crucible results.

Kevin Yu↗

Implementing hydrogen oxidation reaction on Pt for controlling counter electrode processes

The search for active, stable, and durable materials for electrochemical energy technologies requires increasing levels of precision to establish true structure-function relationships and guide materials design from atomic and molecular scale. This increases the level of control required over the experimental system for proper materials evaluation. The choice of counter electrode material become crucial, as Pt dissolution at high voltages may cause contamination to the working electrode, especially when studying reductive processes in reactions such as oxygen reduction reaction (ORR), H 2 evolution reaction (HER), and the CO 2 reduction reaction. The learnings from “old school” electrochemistry groups lead us to leverage H 2 reactions over Pt to construct a counter electrode system with controlled potential that eliminates Pt ion contamination concerns. In here we discuss the construction of such Pt|H 2 counter electrode where key experimental aspects such as the H 2 flow rate and effective distribution determines the maximum current this counter electrode can accommodate before switching to high voltage and triggering Pt dissolution. Lastly, we demonstrate the use of the Pt|H 2 counter electrode in aqueous electrolytes during HER occurring on the working electrode at varying currents, showing that the Pt content in the cell remains below parts per trillion (ppt) up to 10 mA, and below 50 ppt at 100 mA up to 1 h of constant current hold. This work provides a guide to the implementation of Pt|H 2 counter electrodes to improve the precision of electrochemical experiments in search of highly active, selective, and durable materials for energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Activity of Cu-Al-oxo extra-framework clusters for selective methane oxidation on Cu exchanged zeolites

Cu-zeolites are able to directly convert methane to methanol via a 3-step process using O2 as oxidant. Among the different zeolite topologies, Cu-exchanged mordenite (MOR) shows the highest methanol yields, attributed to a preferential formation of active Cu-oxo species in its 8-MR pores. The presence of extra-framework or partially detached Al species entrained in the micropores of MOR leads to the formation of nearly homotopic redox active Cu-Al-oxo nanoclusters with the ability to activate CH4. Studies of the activity of these sites together with characterization by 27Al NMR and IR spectroscopy leads to the conclusion that the active species are located in the 8-MR side pockets of MOR and it consists of two Cu ions and one Al linked by O. This Cu-Al oxo cluster shows an activity per Cu in methane oxidation significantly higher than of any previ-ously reported active Cu-oxo species. In order to determine unambiguously the structure of the active Cu-Al-oxo cluster, we combine experimental XANES of Cu K- and L- edges, Cu K-edge HERFD-XANES and Cu K-edge EXAFS with TDDFT and AIMD-assisted simulations. Our results provide evidence of a [Cu2AlO3]2+ cluster exchanged on MOR Al pairs that is able to oxidize up to two methane molecules per cluster at ambient pressure.

Methane oxidation, Cu L3-edge XANES, HERFD, TDDFT,↗

Competitive Oxidation and Hydration During Aqueous Alteration of Asteroids

Introduction: Studies of chondrites show that incorporation of H2O ice during formation of asteroids followed by radioactive heating caused partial oxidation and hydration of primary reduced and anhydrous rocks. Oxidation of kamacite, phosphides, troilite and organic polymers occurred through consumption of water s oxygen and release of H2. Hydration caused formation of serpentine, saponite, chlorite, talc and hydrated salts. Since H2O was the major reactant in oxidation and hydration, these processes could have been competitive. Redox reactions in asteroids should have been closely connected to hydration (dehydration) during aqueous alteration and thermal metamorphism. For example, dehydration and reduction release H2O that can be consumed in oxidation and hydration, respectively. We model asteroidal processes in order to quantify the fate of H2O and water s oxygen in major redox and hydration/dehydration reactions. Model: Equilibrium compositions in the gas-solid-liquid

Zolotov, M. Y.↗

Advanced Process Control and Dynamic Optimization of Reversible Solid Oxide Cell Systems for Performance and Long-Term Health

This presentation was delivered at the 2024 Hydrogen Annual Merit Review Meeting. It focuses on three aspects of projects focusing on solid oxide cell systems- advanced control including nonlinear model predictive control and traditional control, dynamic optimization with due consideration of chemical degradation over the cell lifetime, dynamic optimization considering physical degradation.

Allan, Douglas↗

Wear-Resistant, Thermally Conductive Coating

Process makes coating with unusual properties. Coating is copper or copper alloy with controlled dispersion of oxide or carbide particles. Process results in coating that has thermal expansion similar to base material, increased resistance to abrasion when hot, and high thermal conductivity. Coatings resistant to wear used in variety of applications ranging from earth-moving equipment to space vehicles.

Edmonds, Brian J.↗

Process for making a noble metal on tin oxide catalyst

A quantity of reagent grade tin metal or compound, chloride-free, and high-surface-area silica spheres are placed in deionized water, followed by deaerating the mixture by boiling and adding an oxidizing agent, such as nitric acid. The nitric acid oxidizes the tin to metastannic acid which coats the spheres because the acid is absorbed on the substrate. The metastannic acid becomes tin oxide upon drying and calcining. The tin-oxide coated silica spheres are then placed in water and boiled. A chloride-free precious metal compound in aqueous solution is then added to the mixture containing the spheres, and the precious metal compound is reduced to a precious metal by use of a suitable reducing agent such as formic acid. Very beneficial results were obtained using the precious metal compound tetraammine platinum(II) hydroxide.

Upchurch, Billy T.↗

Process for Making a Noble Metal on Tin Oxide Catalyst

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Davis, Patricia↗

Molten salt electrolysis and room temperature ionic liquid electrochemical processes for refining rare earth metals: Environmental and economic performance comparison

Circularizing end of life products such as electronic waste can open a new source for rare earth elements (REEs) that will decrease the demand pressure on conventional virgin production. The last step to produce REEs consists of a refining process to convert rare earth oxide (REO) to REE metal. One promising technology is processing REO via a room temperature ionic liquid, which is characterized by low energy requirements in contrast to existing REEs extraction processes. In this work, life cycle and techno-economic assessments are performed and compared against molten salt electrolysis. Here, the results show that both processes have advantages and disadvantages in terms of environmental performance, and that they are similarly competitive in terms of economic performance. A breakeven analysis suggests that future research should focus on coupling the production of REOs with the refining processes to attempt to lower REO cost and make them economically feasible in the U.S.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗