Rare Earth Elements and Actinides: Progress in Computational Science Applications: Chapter 3 Title: Rare Earth Elements and Critical Materials: Uses and Availability
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Penchoff, Deborah↗
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Thermal expansion and phase transformation in the rare earth di-titanate (R 2Ti2O7) system
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99 GENERAL AND MISCELLANEOUS↗
Electrical Control of the Nuclear Spin States of Rare-Earth Adatoms
Rare-earth adatoms on surfaces have been studied for potential atomic-scale magnetic storage, quantum sensing, and quantum computing applications. Despite accumulating experimental efforts, a comprehensive description of the electronic configurations of the adatoms remains elusive. Here, we investigate two charge states and several electronic configurations, including 5d and 6s valence shells, for a Sm adatom on a MgO substrate using multiconfigurational ab initio methods, for the possibility of using the Sm nuclear spin levels as qubits. For the configurations in a neutral charge state, we find that the electronic ground state is a singlet, and thus the hyperfine interaction associated with the 147 Sm nucleus is absent, which may greatly enhance nuclear spin coherence time. The degeneracy of the nuclear levels is lifted by the nuclear quadrupole interaction. We show that the splitting of the nuclear levels can be controlled by a static electric field, and that Rabi oscillations between the nuclear levels can be induced by a time-dependent electric field. For the configurations in a singly charged state, electronic Kramers doublets are formed. The electronic configurations including an unpaired 6s orbital exhibit a strong hyperfine Stark effect due to a large Fermi contact contribution to the hyperfine interaction. In these configurations, electric-field-induced Rabi oscillations between the electronic-nuclear levels can occur at frequencies up to 3 orders of magnitude higher than those for the neutral charge state. The proposed system may be experimentally observed within scanning tunneling microscopy.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Reactive Grinding of Coal Ash For Enhanced Rare Earth Extraction
Monazite and coal ash contain varying trace amounts of Rare Earth Elements (REE). Rare earth elements are considered to be the elements in the lanthanide series. These elements be categorized into two separate groups, light and heavy rare earth groups. Rare Earth Elements play an essential role to society and industry and can be found in a spectrum of applications such as Capacitors, Power Generation, and Catalysts for Petroleum Refining. Due to the abundance of Coal Ash and ongoing production, there is an increasing interest from the scientific community to develop renewable source of energy by extracting rare earth elements from within its contents. Commercial and experimental reactive grinding and leaching procedures have been created to help to maximize the recovery of Rare Earth Elements from Coal Ash.
Keller, Murphy↗
Methods of recovering rare earth elements
A method of recovering a rare earth element. The method comprises dissolving a rare earth element magnetic material in a dissolution organic solvent and a β-diketone compound to form a dissolved rare earth element mixture. A rare earth element of the rare earth element magnetic material and the β-diketone compound are reacted to form a β-diketonate chelate complex and the dissolution organic solvent is removed. The β-diketonate chelate complex is removed using a separation organic solvent, and the β-diketonate chelate complex is recovered. Additional methods are also disclosed.
Klaehn, John R.↗
AN ACID BAKING APPROACH TO ENHANCE RARE EARTH ELEMENT RECOVERY FROM BITUMINOUS COAL SOURCES
Rare earth elements (REE) are a group of 17 elements typically classified as light and heavy rare earth elements, which play a crucial role in developing the latest technologies for energy, defense, and medical sectors. Even though REEs have been found in more than 200 minerals, only bastnaesite, monazite and xenotime are commercially exploited for REE extraction. However, the recent exponential increase in REE demand has spurred countries such as the United States into research for the extraction of REEs from secondary sources such as coal, acid mine drainage, and coal ash. Several coal sources (e.g., Fire Clay seam coal) across the United States have been identified to contain elevated concentrations of rare earth elements (>600 ppm), and various researchers have investigated the feasibility of both physical and hydrometallurgical extraction techniques for rare earth concentration and subsequent extraction. However, both physical and direct leaching were concluded to be inefficient for RE beneficiation and extraction due to low recoveries. Alternatively, thermal treatment provides promising means for RE recovery from bituminous coal sources. The positive impact of thermal treatment/calcination was established to be due to the decarbonization and dehydroxylation of the clays, which released entrapped rare earth elements within the dominant minerals and converted them into an acid-soluble form. Nonetheless, the improvement in recovery was limited to the light REEs (LREEs) with an insignificant increase in the heavy REEs (HREE). It was demonstrated that the light and heavy REEs in the material were associated with difficult-to-leach minerals such as monazite, xenotime, and zircon, which were not decomposed by simple calcination due to their high thermal stability. Hence, roasting in the presence of chemicals was necessary to ensure the decomposition of those REE-containing minerals. As such, this study was focused on the acid baking treatment of bituminous coals with an aim to enhance REE recovery, especially HREEs. Based on the presence of REE minerals like monazite and xenotime, three pre-leach treatment methods, i.e., 1) roasting, 2) direct acid baking, and 3) acid baking after roasting were investigated. Roasting tests at 600 ⁰C revealed that the recovery of light REEs (LREEs) was enhanced while the recovery of HREEs remained relatively unaffected. LREE and HREE recovery values of 38.3% and 21.3%, respectively, were achieved using a 50 g/L sulfuric acid solution at 5% solid concentration and a solution temperature of 75 ⁰C for 2 hours. Comparatively, direct acid baking at 250 °C provided substantial increased LREE and HREE recovery values to approximately 49.4% and 53.0%, respectively, using an equivalent acid dosage. Recoveries were maximized to 77.0% and 79.6% for LREE and HREE, respectively, by roasting followed by acid baking. Similar results were obtained from the treatment of a second bituminous coal source. Due to strong correlations between REE and Al recovery values, tests were performed on kaolinite and illite, which were prominent clay minerals within the source coals. These experiments revealed that the REE recovery improvements were likely a result of dehydroxylation of clays and subsequent release and decomposition of REE-bearing minerals such as monazite, xenotime and zircon. Subsequently, a parametric study was conducted to identify the impact of acid baking parameters on rare earth element recovery. The factors investigated using a three-level statistical experimental program were acid baking time, acid solution concentration, baking temperature, and acid solution-to-solids ratio which were found to significantly impact REE and contaminant element (Al, Fe, and Ca) recovery. An increase in baking temperature up to around 250 ⁰C improved the light and heavy REE recovery values by more than 50 absolute percentage points relative to performances achieved when direct leaching. As aforementioned, acid baking was needed to both decompose the clay minerals and liberate the REE minerals, which allowed access for the acid to solubilize the REEs. Acid concentration of the solution used for acid baking was studied as a means of minimizing the amount of acid needed to achieve a target REE recovery. However, thermo-gravimetric and differential scanning calorimetry analysis (TGA-DSC) of sulfuric acid under oxidizing atmosphere revealed that the addition of water decreased the evaporation temperature, which explains the lower REE recovery values obtained when using acid concentrations less than 100%. Using pure sulfuric acid at an acid-to-solid ratio of 0.8:1 resulted in recovery values of around 70% for both LREEs and HREEs. The decomposition reaction time was relatively quick with 65% of the TREEs recovered within the first 10 minutes. Following the identification of optimum operating conditions through the parametric study, a systematic leaching study was carried out to examine the impact of leaching parameters, such as solid-to-liquid (S/L) ratio, temperature, and time, on REE recovery using acid baking conditions of 1:1 acid to solids ratio at 250 °C for 30 minutes. The solid-to-liquid ratio was varied from 1-20% by weight at 25 °C, 50 °C, and 75 °C solution temperatures. The results indicated that reaction time and solution temperature considerably impacted the recovery of heavy and light REEs. Interestingly, LREE recovery reduced from 68% at 5% S/L to 58% at 20%S/L, whereas HREE recovery of 78% remained unaffected. The decrease in the LREE recovery was determined to be due to La and Ce precipitation, likely through isomorphic substitution with calcium in gypsum. The kinetic data indicated that 67% LREE and 77% HREE recovery could be obtained within the first 15 minutes of the reaction, suggesting fast reaction kinetics. Furthermore, raising the solution temperature from 25 °C to 75 °C increased the LREE and HREE recovery from 60% and 32% to 67% and 79%, respectively. The kinetic modeling results demonstrated that the rate-limiting step in the LREE dissolution was diffusion and chemical reaction, whereas the HREE extraction was controlled by only chemical reaction. The leaching study concluded that using 20% S/L at 75 °C for 15 minutes maximized LREE and HREE recovery. The lab-scale precipitation study showed that Fe and Al in solution could be removed at pH 4.5 followed by REE precipitation at pH 6.0 using 6 mol/L NaOH. Finally, the bench-scale data was used to develop a process flowsheet for REE recovery from low-grade bituminous coal sources using acid baking. Finally, based on the proposed flowsheet, a concentrated RE-cake obtained through selective precipitation at pH 6.5 was re-leached using HCl at pH 1.5. The resultant leachate was used to identify the impact of various operating parameters on REE recovery and purity with an aim to maximize REE precipitation efficiency while minimizing the oxalic acid dosage. The operating parameters for this investigation were oxalic acid dosage, iron (III) contamination, solution pH and temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicated that increasing the oxalic acid concentration from 0g/L to 80g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. The speciation analysis revealed that the dominant iron species in the solution system were Fe-(C₂O₄)₃³⁻, Fe-(C₂O₄)²⁻, and Fe-(C₂O₄)⁺, which consumed the majority of the oxalate anions
rare earth elements, acid baking, high-temperature↗
Achieving American Leadership in the Rare Earth Magnets Supply Chain Factsheet
Rare earth permanent magnets are a critical technology for the clean energy transition and electrified transport revolution. The global supply chain for rare earth metals and magnets is almost completely dominated by China, which controlled 58% of rare earth mining and 92% of magnet manufacturing in 2020. The United States produces only 15% of the global supply of raw materials for these magnets, and while the nation has several nascent downstream processing and manufacturing efforts, current domestic production is limited. Investments and incentives to boost the domestic supply chain, especially in the separation and refining phases, point the way to securing stable supplies of these critical clean energy components.
Source record↗
How Cerium and Lanthanum as Coproducts Promote Stable Rare Earth Production and New Alloys
The largest outputs of rare earth mining are the low-value byproducts cerium and lanthanum, which burden rare earth supply chains because they must be separated from more desirable rare earths used in magnet production. Promoting demand for cerium and lanthanum can potentially diversify the economics of rare earth mining and improve supply chain stability for all rare earth elements. A promising avenue for increasing byproduct rare earth element demand is their use in aluminum alloys; an application for cerium and lanthanum offering multiple benefits to manufacturing such as energy reduction and improved throughput. Experimental materials science and economic implications of Al-rare earth element alloys will be discussed. We show that Al–La/Ce alloys have elevated mechanical strength compared to more traditional aluminum alloys, in some formulations can be used without heat treatment, and possess a highly castable eutectic microstructure. This report presents the use of cerium and lanthanum in aluminum alloys as an example of how supply chain focused approaches to technological development can benefit stakeholders at every step in production.
36 MATERIALS SCIENCE↗
Metal-Dependent Photodissociation of Hydrazone Photoswitches from Rare-Earth Complexes
Rare-earth element separation processes often rely on a small decrease in ionic radii along the series of elements. Separation processes based on the distinct optical properties of REs remain less explored, although photochemical methods may offer a viable alternative. Accurate selection of the synthetic precursors of a photoswitchable acylhydrazonic ligand led to a system that could quantitatively isomerize (E−to−Z) upon irradiation with commercial LED lights. Coordination of the photoswitch with RE III nitrates (RE = La−Lu except Pm and Y) resulted in the retention of the photoswitching properties observed in solution. The lower binding affinity of the generated Z−isomer with RE III ions yielded the dissociation of the complexes upon irradiation (photodissociation) with the release of RE−nitrates in solution. The rate of the reaction was found to be dependent on the optical properties of the RE III ions, with nonemissive complexes (no 4f excited states) dissociating faster than emissive ones (having accessible 4f excited states). A thorough solid-state characterization of the complexes was performed by using crystallographic and photochemical methods. Ultimately, the accessibility of the 4f excited states of the metals following light irradiation and excitation of the ligand led to a decrease in the rate of the reaction due to quenching of the ligand excited state. These results demonstrate that the direct modulation of the metal coordination environment, combined with the metal-dependent reaction rate, could provide a strategy for the development of RE−separation processes based on differences in their optical properties.
Ions↗
Signatures of polarized chiral spin disproportionation in rare earth nickelates
In rare earth nickelates (RENiO 3 ), electron-lattice coupling drives a concurrent metal-to-insulator and bond disproportionation phase transition whose microscopic origin has long been the subject of active debate. Of several proposed mechanisms, here we test the hypothesis that pairs of self-doped ligand holes spatially condense to provide local spin moments that are antiferromagnetically coupled to Ni spins. These singlet-like states provide a basis for long-range bond and spiral spin order. Using magnetic resonant X-ray scattering on NdNiO 3 thin films, we observe the chiral nature of the spin disproportionated state, with spin spirals propagating along the crystallographic (101) ortho direction. These spin spirals are found to preferentially couple to X-ray helicity, establishing the presence of a hitherto-unobserved macroscopic chirality. The presence of this chiral magnetic configuration suggests a potential multiferroic coupling between the noncollinear magnetic arrangement and improper ferroelectric behavior as observed in prior studies on NdNiO 3 (101) ortho films and RENiO 3 single crystals. Experimentally constrained theoretical double-cluster calculations confirm the presence of an energetically stable spin-disproportionated state with Zhang-Rice singlet-like combinations of Ni and ligand moments
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
High-throughput screening for discovery of benchtop separations systems for selected rare earth elements
Abstract Rare earth (RE) elements (scandium, yttrium, and the lanthanides) are critical for their role in sustainable energy technologies. Problems with their supply chain have motivated research to improve separations methods to recycle these elements from end of life technology. Toward this goal, we report the synthesis and characterization of the ligand tris[(1-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamido)ethyl]amine, H 3 1·TFA (TFA = trifluoroacetic acid), and complexes 1·RE (RE = La, Nd, Dy). A high-throughput experimentation (HTE) screen was developed to quantitatively determine the precipitation of 1·RE as a function of pH as well as equivalents of H 3 1·TFA. This method rapidly determines optimal conditions for the separation of RE mixtures, while minimizing materials consumption. The HTE-predicted conditions are used to achieve the lab-scale separation of Nd/Dy ( SF Nd/Dy = 213 ± 34) and La/Nd ( SF La/Nd = 16.2 ± 0.2) mixtures in acidic aqueous media.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Correlation effects on coupled electronic and structural properties of doped rare-earth trihydrides
Rare-earth trihydride (𝑅H 3 ) compounds exhibit intriguing coupled electronic and structural properties as a function of doping, hydrogen vacancies, and thermodynamic conditions. Theoretical studies of these materials typically rely on density functional theory (DFT), including the use of small supercells that may underestimate strong correlation effects and structural distortions which in turn may influence their metallicity. Here, we elucidate the roles of lattice distortions and correlation effects on the electronic properties of pristine and doped 𝑅H 3 compounds by adopting DFT +U and quantum Monte Carlo (QMC) methods. Linear-response constrained DFT (LR-cDFT) methods find Hubbard U ≈ 2 eV for 𝑅 𝑑 orbitals and U ≈ 6 eV for H 𝑠 /N 𝑝 /O 𝑝 orbitals. The small U on Lu 𝑑 orbitals is consistent with QMC calculations on LuH 3 and LuH 2.875 N 0.125 . In pure face-centered-cubic (FCC) 𝑅H 3 (𝑅 = Lu,Y) compounds, neither DFT nor DFT +U with the self-consistently determined U is enough to create a band gap, however a supercell with hydrogen distortions creates a small gap whose magnitude increases when performing DFT +U with self-consistently determined U values. Furthermore, correlation effects, in turn, have a moderate influence on the coupled structural and electronic properties of doped 𝑅H 3 compounds and may be important when considering the competition between structural distortions and superconductivity.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Sublattice-Dependent Antiferromagnetic Transitions in Rare Earth Nickelates
Perovskite rare earth nickelates exhibit remarkably rich physics in their metal-insulator and antiferromagnetic transitions, and there has been a long-standing debate on whether their magnetic structures are collinear or noncollinear. Through symmetry consideration based on the Landau theory, we discover that the antiferromagnetic transitions on the two nonequivalent Ni sublattices occur separately at different Néel temperatures induced by the O breathing mode. It is manifested by two kinks on the temperature-dependent magnetic susceptibilities with the secondary kink being continuous in the collinear magnetic structure but discontinuous in the noncollinear one. Here, the prediction on the secondary discontinuous kink is corroborated by an existing magnetic susceptibility measurement on bulk single-crystalline nickelates, thus strongly supporting the noncollinear nature of the magnetic structure in bulk nickelates, thereby shedding new light on the long-standing debate.
36 MATERIALS SCIENCE↗
Process-based cost estimation framework for assessing economic viability of environmentally and socially sustainable rare earth element feedstocks
Rare Earth Elements (REEs) are critical raw material inputs that are required to enable the energy transition. Constraints on the U.S. supply of conventional REE feedstocks and the desire to diversify U.S. reliance on foreign supply chains have motivated the pursuit of REE recovery from unconventional feedstocks including waste products. Recovery of REEs from unconventional sources is also motivated by environmental and social considerations, including the potential to offset new mining activity and subsidize the remediation of REE-containing wastes from coal, natural gas, and other mineral extraction activities. Sourcing REEs from unconventional feedstocks would reduce supply chain constraints and minimize the environmental impacts of REE extraction, but current processes to exploit these feedstocks have uncertain technical and economic performance and the processes have not been demonstrated at scale. This work aims to reduce uncertainty in evaluating the performance of new REE production pathways. A database of operating and capital expenses for REE recovery and establish consistent process unit costs for common stages in the conventional supply chain are developed. Market prices are used to develop well-defined methods for determining product values for a diverse set of products that can be generated (e.g. oxalates, alloys, end-use products such as magnets) but are not typically considered in technoeconomic analyses. Finally, to provide insight on the effects of economies of scale and feedstock purity on capital and operating costs, process unit level cost functions relating total costs per kilogram of REE produced are reported. These tools can be applied to assess and facilitate scale-up of REE production from diverse sources of REEs.
Fritz, Alison↗
Rare Earth Elements and Actinides: Progress in Computational Science Applications Chapter 1 Title: An Introduction to High Performance Computing and Its Intersection with Advances in Modeling Rare Earth Elements and Actinides
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Penchoff, Deborag↗
System and method for predicting the presence of rare earth elements
A system for predicting rare earth elements (REEs) in a feedstock sample includes a measurement instrument that records a measurement for a sample, a processor communicatively coupled to the measuring instrument, and a memory communicatively coupled to the processor and containing machine readable instructions that, when executed by the processor, cause the processor to correlate the measurement series using a model; and predict a presence of one or more rare earth element based at least in part on the correlation. A method for predicting rare earth elements includes measuring feedstock samples via XRF or PGNAA, to generate a measurements of elements of interest with a lower atomic weight than REEs; correlating the measurements with a model; and predicting a presence of one or more rare earth elements based at least in part on the correlation.
Fuka, Matthew↗