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Results for “Rare Earth Synthesis”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Diethylenetriamine-functionalized graphene oxide: Insights into ion adsorption and applications in rare earth element separation

The growing demand for critical minerals and materials requires atom- and energy-efficient, selective separations to overcome the challenges posed by the similar chemical and physical properties of the rare earth elements (REEs) and their low concentrations in unconventional domestic feedstocks. Here, in this study, we developed diethylenetriamine-functionalized graphene oxide (DETA-GO) as a membrane material for REE adsorption and separation. Synthesis conditions were optimized to maximize nitrogen incorporation while also preserving GO dispersibility for facile membrane fabrication. We investigated the mechanism of amine functionalization, the nitrogen-bonding configurations, the organization of the interlayer transport channels, and the resulting effects on ion and water transport for REE separations. Neat-GO and DETA-GO multilayer laminate membranes were fabricated by vacuum filtration onto polymer supports. To investigate the effects of amine functionalization, the membranes were characterized using scanning electron microscopy, Raman, Fourier transform infrared, and X-ray photoelectron spectroscopy, as well as grazing-incidence X-ray diffraction measurements. Ion permeation experiments with representative lanthanum (La 3+ ) and ytterbium (Yb 3+ ) solutions revealed enhanced ion adsorption and water transport through DETA-GO membranes compared to neat-GO. The strong affinity of the membranes for multivalent REEs was also validated with conductivity and inductively coupled plasma mass spectrometry measurements. Atomistic insight into the role of amine functionalization in modulating nanochannel architecture and long-term stability, optimizing adsorption sites, and regulating REE and water transport was obtained using classical molecular dynamics simulations. Collectively, our joint experimental and theoretical study demonstrates the potential of DETA-GO membranes for selective REE separations, offering insights into ion-binding mechanisms, water-transport properties, and nanochannel optimization for the recovery of critical materials from aqueous feedstocks.

Adsorbent↗
DOE OSTI2023

Thorium and Rare Earth Monoxides and Related Phases

Thorium was a part of energy infrastructure in the 19th century due to the refractory and electronic properties of its dioxide. It will be a part of future energy infrastructure as the most abundant energy reserve based on nuclear fission. This paper discusses the solid-state chemistry of the monoxides and related rocksalt phases of thorium and the rare earths, both at atmospheric and at high pressure. The existence of solid thorium monoxide was first suggested more than 100 years ago; however, it was never obtained in bulk and has been studied mostly theoretically. Monoxides of lanthanides from Eu to Ho are ferromagnetic semiconductors sought for spintronics and were studied in thin films. La to Sm metallic monoxides were synthesized in bulk at pressures below 5 GPa. Recently, ThO formation in thin films has been reported and the stability of bulk ThO at high pressure was theoretically predicted based on first principles computations at 0 K. New ab initio computations were performed accounting for temperature effects up to 1000 K using lattice dynamics in the quasi-harmonic approximation. New computational results confirm the stabilization of pure ThO above 30 GPa and suggest the possibility of high-pressure synthesis of (Th,Nd)O at 1000 K and 5 GPa.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Synthesis and magnetic performance of gadolinium powder produced with rotating disk atomization

Spherical powder is key for achieving good heat transfer and maintaining low pressure drop for heat transfer fluid in magnetocaloric regenerator. Obtaining relatively large spherical powder of rare earth metals that are extremely sensitive to oxygen is challenging. Comparing to gas atomization and plasma rotating electrode methods, rotating disk atomization (RDA) method is more robust for obtaining a small amount of powder with a short turn-around time, thereby, more suitable for research and development of new magnetocaloric materials. In this work, commercially bulk gadolinium was successfully atomized to produce spherical powder in the targeted 150–250 μm range. The obtained powder exhibited the expected magnetocaloric performance with a maximum change of magnetic entropy of 12.1 J/kg K and a maximum adiabatic temperature change of 12.8 K with an applied magnetic field of 7 T.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Unusual 5f magnetism in new kagome material UV 6 Sn 6

Materials in the family R V 6 Sn 6 (R = rare earth) provide a unique platform to investigate the interplay between local moments from R layers and nonmagnetic vanadium kagome layers. Yet, the investigation of actinide members remains scarce. Here we report the synthesis of UV 6 Sn 6 single crystals through the self-flux technique. Physical property measurements reveal two uranium-driven antiferromagnetic transitions at T N 1 = 29 K and T N 2 = 24 K, a complex field-temperature phase diagram, and unusual negative domain-wall magnetoresistance. Specific heat and angle-resolved photoemission spectroscopy measurements show a moderate f -electron enhancement to the density of states at the Fermi level (EF), whereas our band structure calculations place the vanadium flat bands 0.25 eV above E F . These findings point to a materials opportunity to expand the uranium 166 family with the goal of enhancing correlations by tuning 5 f and 3 d flat bands to E F .

36 MATERIALS SCIENCE↗
DOE OSTI2022

Adapting UFF4MOF for Heterometallic Rare-Earth Metal–Organic Frameworks

Heterometallic metal–organic frameworks based on rare-earth metals (RE-MOFs) have potential in a number of applications where energy transfer between nearby metal atoms is required. This observation implies that it is important to understand the level of local mixing that is achieved between metals of different types during synthesis of RE-MOFs. Density functional theory calculations can give quantitative information on the relative energy of different configurations of RE-MOFs, but these calculations cannot be applied to the full range of medium- and long-range orderings that are possible in heterometallic materials. This limitation can be overcome using force field (FF)-based calculations if appropriate FFs are available. In this work, we show that an existing generic FF for MOFs, UFF4MOF, does not accurately predict energies of mixing in heterometallic Nd/Yb MOFs and introduce a modified FF to address this shortcoming. The resulting FF is used to explore metal orderings in large simulation volumes for a Nd/Yb MOF, illustrating the complexities that can arise in the structure of heterometallic RE-MOFs.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermochemistry of sodium rare earth ternary fluorides, NaREF 4

Sodium rare earth fluorides, NaREF 4 (RE = rare earth), are used as luminescent materials for light emission and biomedical applications and are important compositions for extracting and separating RE elements. Solution calorimetric measurements of a series of β-structured NaREF 4 (Na 1.5 RE 1.5 F 6 ) phases with various RE elements determined their heats of formation. Though the lattice contracts from light to heavy RE elements, NaREF 4 compounds show more exothermic enthalpies of formation from binary components with the decrease of RE 3+ radii, contrary to behavior seen in most RE oxide ternary compounds. Furthermore, by constructing Born–Haber cycles, the different slopes of lines relating lattice energies to lattice parameters in binary and ternary fluorides appear to be the reason for this reverse trend, which can be associated with changes in the coordination number of RE cations. These trends and the metastability of sodium light RE fluorides not only reveal the key role of ionic radius in RE compound stability, but also are significant for the design and synthesis of new materials and motivate the more effective utilization of RE.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Structurally Defined Water‐Soluble Metallofullerene Derivatives towards Biomedical Applications

Abstract Endohedral metallofullerenes (EMFs) are excellent carriers of rare‐earth element (REE) ions in biomedical applications because they preclude the release of toxic metal ions. However, existing approaches to synthesize water‐soluble EMF derivatives yield mixtures that inhibit precise drug design. Here we report the synthesis of metallobuckytrio (MBT), a three‐buckyball system, as a modular platform to develop structurally defined water‐soluble EMF derivatives with ligands by choice. Demonstrated with PEG ligands, the resulting water‐soluble MBTs show superb biocompatibility. The Gd MBTs exhibit superior T 1 relaxivity than typical Gd complexes, potentially superseding current clinical MRI contrast agents in both safety and efficiency. The Lu MBTs generated reactive oxygen species upon light irradiation, showing promise as photosensitizers. With their modular nature to incorporate other ligands, we anticipate the MBT platform to open new paths towards bio‐specific REE drugs.

Li, Yanbang↗
DOE OSTI2020

Development of Mischmetal–Fe–Co–B Permanent Magnet Alloys via High-Throughput Methods

Additive manufacturing synthesis using laser engineered net shaping (LENS) is utilized in this work to rapidly print libraries of mischmetal (MM = La, Ce, Nd, and Pr) containing R 2 TM 14 B alloys (R = MM + separated Nd and TM = Fe and Co) enabling robust evaluation of physical properties over a wide composition range. High-throughput characterization of the magnetic and thermal properties are used to identify compositions for potential high-temperature, high-performance permanent magnets with reduced critical rare-earth elements. Improved Curie temperature ( T c ~ 450 °C) is obtained with substitution of Fe by Co in pseudoternary R 2 TM 14 B alloys. Furthermore, a 4-fold decrease in the Nd content can be achieved through substitution with less critical Ce- and La-rich MM, while retaining high T c . Guided by the properties of the LENS printed samples, selected compositions with and without TiC additions are synthesized via melt-spinning techniques to produce nanostructured ribbons. The maximum room temperature coercivity ( H c ) and energy product ((BH) max ) without TiC are found to be 5.8 kOe, 8.5 MGOe, respectively, while TiC additions as a grain refiner gave H c and (BH) max of 4.9 kOe, 9.8 MGOe, respectively. Structural characterization of the melt-spun ribbons shows homogeneous grain refinement with TiC additions, which leads to an increase in the energy product.

36 MATERIALS SCIENCE↗
DOE OSTI2023

L1 0 Ordering in MnAl and FeNi Influenced by Magnetic Field and Strain

Due to various materials supply chain challenges, magnets free of constrained elements are attracting increasing interest. Magnetic materials such as rare-earth free FeNi and MnAl have been receiving considerable attention due to the high magnetocrystalline anisotropy and other associated magnetic properties derived from their unique chemically ordered tetragonal crystal structure, denoted as the L1 0 structure. However, synthesis of L1 0 FeNi has had limited success due to the extremely low atomic mobilities of Fe and Ni. In this work, isostructural MnAl was first studied as proxy to understand the L1 0 ordering process. Here, evidence of L1 0 ordering in FeNi derived from TEM studies is presented, where ordering was facilitated by the application of strain and magnetic field provided during thermal treatment of a severely plastically deformed FeNi alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Self-healing Growth of LaNiO 3 on a Mixed-Terminated Perovskite Surface

Developing atomic-scale synthesis control is a prerequisite for understanding and engineering the exotic physics inherent to transition-metal oxide heterostructures. Thus, far, however, the number of materials systems explored has been extremely limited, particularly with regard to the crystalline substrate, which is routinely SrTiO 3 . Here, we investigate the growth of a rare-earth nickelate-LaNiO 3 -on (LaAlO 3 )(Sr 2 AlTaO 6 ) (LSAT) (001) by oxide molecular beam epitaxy (MBE). Whereas the LSAT substrates are smooth, they do not exhibit the single surface termination usually assumed necessary for control over the interface structure. Performing both nonresonant and resonant anomalous in situ synchrotron surface X-ray scattering during MBE growth, we show that reproducible heterostructures can be achieved regardless of both the mixed surface termination and the layer-by-layer deposition sequence. The rearrangement of the layers occurs dynamically during growth, resulting in the fabrication of high-quality LaNiO 3 /LSAT heterostructures with a sharp and consistent interfacial structure. This is due to the thermodynamics of the deposition window as well as the nature of the chemical species at interfaces-here, the flexible charge state of nickel at the oxide surface. This has important implications regarding the use of a wider variety of substrates for fundamental studies on complex oxide synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Quantification of zwitterion betaine in betaine bis(trifluoromethylsulfonyl)imide and its influence on liquid–liquid equilibrium with water

In this study, ionic liquids (ILs) have been proposed as extractants for separation of metals, including rare earth elements. In particular, protonated betaine bis(trifluoromethylsulfonyl)imide ([HBet][TFSI]) exhibits liquid–liquid phase behavior with water that can be tuned by complexation with various metals. Here we show that previously undetected neutral zwitterionic betaine formed during the IL synthesis can affect the phase behaviour. Traditional synthesis of protonated betaine bis(trifluoromethylsulfonyl)imide results in significant amounts of neutral zwitterionic betaine impurity, which dramatically affects phase behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enhancing stability, magnetic anisotropy, and coercivity of manganese aluminum: Machine learning, ab initio , and micromagnetic modeling

The binary manganese aluminum (MnAl) alloy with L⁢1 0 crystal structure is a promising rare earth (RE) element-free permanent magnetic material because of its exceptional magnetic properties. However, experimentally synthesizing it in a stable bulk form is extremely challenging. Here, in this study, an alternative method of stabilizing the material, a pathway for experimental synthesis and validation, is proposed and theoretically verified. This is done by partially substituting Mn and Al sites with Fe and Ni and identifying its enhanced phase stability, saturation magnetization density, magnetic anisotropy, and coercivity from density functional theory (DFT), machine learning (ML) crystal graph convolution neural network (CGCNN), and micro-magnetic modeling. When considering a fixed 50% Ni, the magnetic anisotropy increases with the increasing Fe content but decreases the formation energy. The calculated formation energies, elastic constants, and phonon frequencies demonstrate that the binary and quaternary compositions are stable. Most importantly, in 50% Fe and Ni-substituted-equiatomic phase, magnetic anisotropy constants and saturation magnetization density increase by 56% and 23% as compared to the MnAl. Further, the coercivity of the equiatomic phase predicted with micro-magnetic modeling is higher by 17% than the parent compound.

Bhandari, Churna [Ames National Laboratory, and Io↗
DOE OSTI2023

Prediction and Control of Atomic Ordering in Electrodeposited Binary Alloy Films: Direct Synthesis of L10 Magnetic Phases

Permanent magnet materials are essential components in renewable energy technology, underlying, electric vehicles, hybrids, wind turbines and more. Today commercial permanent magnets based on Nd-Fe-B exhibit an energy product of ~ 400 kJ/m 3 , capable to run wind turbines efficiently. Unfortunately, the supplies of rare-earth elements are centralized, and their availability may see volatility over time. This state of affairs stimulates the search for the search for rare-earth-free permanent magnetic materials. The L1 0 crystal structure underlines an important class of chemical ordered alloys that exhibit uniaxial magnetocrystalline anisotropy. This material has been considered an excellent candidate for rare-earth-free permanent magnets. In this program, a series of systematic experiments were performed and analysed in order to understand the effect of each. In order to synthesize L 10-Fe-Ni, one has to circumvent the sluggish kinetic and the limited driving force resulted from the low order-disorder temperature (~320°C) of the system. A strategy was found to trigger a martensitic transformation from the FCC phase to one of the non-cubic phases by high-strain methods. The body-centered tetragonal Fe-Ni obtained by this strategy was considered as a precursor of L10 Fe-Ni. The formation of BCT Fe-Ni via a displacive process was also implemented at the nanoscale by using tailored AuNi@FeNi core@shell.

36 MATERIALS SCIENCE↗
DOE OSTI2020

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↗
DOE OSTI2021

Structural, vibrational, thermal, and magnetic properties of mullite-type NdMnTiO 5 ceramic

Mullite-type $R$Mn 2 O 5 ($R$ = Y, rare-earth element) ceramics are of ongoing research attention because of their interesting crystal-chemical and magnetic properties. We report nuclear and magnetic structures of NdMnTiO 5 together with its spectroscopic, thermogravimetric, and magnetic properties. The polycrystalline sample is prepared by solid-state synthesis and characterized from neutron and X-ray powder diffraction data Rietveld refinements. NdMnTiO 5 crystallizes in the orthorhombic space group $Pbam$ with metric parameter $a$ = 755.20(1) pm, $b$ = 869.91(1) pm, $c$ = 582.42(1) pm, and $V$ = 382.62(1) 10 6 pm 3 . The Mn 3+ and Ti 4+ cations are observed to be located in the octahedral and pyramidal sites, respectively. The vibrational features in these polyhedral sites are characterized by Raman and Fourier transform infrared spectroscopes. The higher decomposition temperature of NdMnTiO 5 , compared to other $R$Mn 2 O 5 phases, is explained in terms of the higher bond strength of Ti-O bonds than those of Mn-O bonds. Temperature-dependent DC magnetic susceptibility suggests a paramagnetic to antiferromagnetic phase transition at 43(1) K. Inverse susceptibility in the paramagnetic region above 120 K follows the Curie-Weiss law, resulting in a magnetic moment of 6.33(1) μ B per formula unit. Neutron diffraction data collected at 7.5 K reveal that the magnetic moments of Nd 3+ and Mn 3+ in NdMnTiO 5 are incommensurately ordered with a propagation vector $k$ = (0, 0.238, 0.117).

36 MATERIALS SCIENCE↗
DOE OSTI2025

Nickel Enhances InPd-Catalyzed Nitrate Reduction Activity and N 2 Selectivity

Palladium–indium (PdIn) is a well-established bimetallic composition for reductively degrading nitrate anions, one of the most ubiquitous contaminants in the groundwater. However, the scarcity and the variable price of these rare-earth and platinum group critical metals may hinder their use for water treatment. Nickel (Ni), a nonprecious metal in the same element group as Pd, could partially replace and lower Pd usage if the resulting trimetallic composition is sufficiently catalytically active. Herein, we report the synthesis and nitrate reduction catalysis of activated carbon-supported “In-on-Pd-on-Ni” catalysts (InPdNi/AC). While bimetallic InPd/AC (0.05 wt % In, 1.3 wt % Pd) was expectedly active, trimetallic InPdNi/AC containing the same In amount, much less Pd (0.1 wt %), and 1 wt % Ni was >17 more active (k cat ≈ 20 vs 349 L min –1 g surface metal –1 ). X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations showed that Pd gained electron density from Ni, correlating to the increased nitrate reduction activity. Ammonium byproduct selectivity for InPdNi/AC (18% at 50% nitrate conversion) was lower compared to that of InPd/AC (48%), suggestive of the higher surface coverage of NO or its greater reactivity with NO 2 – , which led to more N 2 . Accounting for the catalyst precursor, manufacturing costs, and spent metal recovery, we calculated that Ni incorporation lowered the net catalyst cost significantly (from $\$$1028/kg to $\$$170/kg). The trimetallic composition lowered, by ∼26 times, the catalyst cost of a stirred tank reactor sized to the same treatment capacity as that for the bimetallic case. In conclusion, the results demonstrate that the partial replacement of the precious metal with an earth-abundant one leads to a higher efficiency and lower cost denitrification catalyst, via a material strategy that should be beneficial for other clean-water catalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Architector for high-throughput cross-periodic table 3D complex building

Abstract Rare-earth and actinide complexes are critical for a wealth of clean-energy applications. Three-dimensional (3D) structural generation and prediction for these organometallic systems remains a challenge, limiting opportunities for computational chemical discovery. Here, we introduce Architector , a high-throughput in-silico synthesis code for s-, p-, d-, and f-block mononuclear organometallic complexes capable of capturing nearly the full diversity of the known experimental chemical space. Beyond known chemical space, Architector performs in-silico design of new complexes including any chemically accessible metal-ligand combinations. Architector leverages metal-center symmetry, interatomic force fields, and tight binding methods to build many possible 3D conformers from minimal 2D inputs including metal oxidation and spin state. Over a set of more than 6,000 x-ray diffraction (XRD)-determined complexes spanning the periodic table, we demonstrate quantitative agreement between Architector-predicted and experimentally observed structures. Further, we demonstrate out-of-the box conformer generation and energetic rankings of non-minimum energy conformers produced from Architector , which are critical for exploring potential energy surfaces and training force fields. Overall, Architector represents a transformative step towards cross-periodic table computational design of metal complex chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thin film combinatorial sputtering of Al-Ce alloys: Investigating the phase separation of as-deposited solid solutions and determining the coefficient of thermal expansion

Al x Ce 100–x thin films with a composition range of ~75.0 < x < 99.5 at% (36.5 < x < 97.5 wt%) were synthesized via combinatorial co-sputtering from an Al and an Al 50 Ce 50 target. The crystal structure, phase fraction, film morphology, electrical resistivity, and temperature-dependent coefficients of thermal expansion (CTE) are all correlated to the Al x Ce 100–x composition. The as-deposited films form a metastable solid-solution, and annealing leads to the formation of the thermodynamically stable two-phase system of Al and the α-Al 11 Ce 3 intermetallic. Temperature dependent x-ray diffraction (XRD) reveals that the two phases expand independently of one another, and the thin film Al temperature-dependent CTE is similar to bulk Al. The thin film Al 11 Ce 3 intermetallic phase has a nearly constant CTE of ~1.5 × 10 –5 /°C within the temperature range studied (25–550 °C). To confirm the thin film Al 11 Ce 3 results, bulk stoichiometric Al 11 Ce 3 and +/- 1 wt% Ce samples were prepared and the CTE of each was measured with the same conditions. A Rietveld analysis of the bulk data enabled an estimation of the CTE in each of the 3 orthorhombic lattice parameters, which displayed anisotropic behavior. The thin film and bulk CTE measurements were in very good agreement. Estimations of the temperature dependent CTE of the two-phase alloys are made via the Reuss and Voigt models. Finally, by demonstrating the efficacy of the approach, more complex multi-component rapid materials discovery of low CTE Al-alloys can be pursued via the combinatorial thin film synthesis and XRD measurement.

36 MATERIALS SCIENCE↗