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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Genomic characterization of rare earth binding by Shewanella oneidensis

Abstract Rare earth elements (REE) are essential ingredients of sustainable energy technologies, but separation of individual REE is one of the hardest problems in chemistry today. Biosorption, where molecules adsorb to the surface of biological materials, offers a sustainable alternative to environmentally harmful solvent extractions currently used for separation of rare earth elements (REE). The REE-biosorption capability of some microorganisms allows for REE separations that, under specialized conditions, are already competitive with solvent extractions, suggesting that genetic engineering could allow it to leapfrog existing technologies. To identify targets for genomic improvement we screened 3,373 mutants from the whole genome knockout collection of the known REE-biosorbing microorganism Shewanella oneidensis MR-1. We found 130 genes that increased biosorption of the middle REE europium, and 112 that reduced it. We verified biosorption changes from the screen for a mixed solution of three REE (La, Eu, Yb) using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) in solution conditions with a range of ionic strengths and REE concentrations. We identified 18 gene ontologies and 13 gene operons that make up key systems that affect biosorption. We found, among other things, that disruptions of a key regulatory component of the arc system ( hptA ), which regulates cellular response to anoxic environments and polysaccharide biosynthesis related genes ( wbpQ , wbnJ , SO_3183 ) consistently increase biosorption across all our solution conditions. Our largest total biosorption change comes from our SO_4685 , a capsular polysaccharide (CPS) synthesis gene, disruption of which results in an up to 79% increase in biosorption; and nusA, a transcriptional termination/anti-termination protein, disruption of which results in an up to 35% decrease in biosorption. Knockouts of glnA , pyrD , and SO_3183 produce small but significant increases (≈ 1%) in relative biosorption affinity for ytterbium over lanthanum in multiple solution conditions tested, while many other genes we explored have more complex binding affinity changes. Modeling suggests that while these changes to lanthanide biosorption selectivity are small, they could already reduce the length of repeated enrichment process by up to 27%. This broad exploratory study begins to elucidate how genetics affect REE-biosorption by S. oneidensis , suggests new areas of investigation for better mechanistic understanding of the membrane chemistry involved in REE binding, and offer potential targets for improving biosorption and separation of REE by genetic engineering.

Medin, Sean↗
DOE OSTI2026

Design and optimization of processes for recovering rare earth elements from end‐of‐life permanent magnets

Recovery of rare earth elements (REEs) from end-of-life (EOL) products represents a strategic opportunity to strengthen the domestic supply chain for rare earth elements. This work presents a superstructure-based optimization framework for finding the most economical processing pathway for different EOL rare earth permanent magnets (REPMs). The framework evaluates state-of-the-art technologies across four processing stages—disassembly, demagnetization, leaching and extraction, and precipitation and calcination—using net present value (NPV) maximization and cost of recovery (COR) minimization objectives. A novel bottom-up costing framework for hydrogen decrepitation is also introduced. Two feedstocks were considered: REPMs from EOL hard disk drives (HDDs), and electric and hybrid electric vehicles (EVs and HEVs). While HDD recycling proved unprofitable due to limited feedstock availability, EVs/HEVs were profitable across a range of parameters and cost estimates. Therefore, our findings suggest that the proposed EOL EV/HEV recycling process may be economical and is worthy of further investigation.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2023

From ash to oxides: Recovery of rare-earth elements as a step towards valorization of coal fly ash waste

Coal fly ash (CFA) is both a valuable waste material and a potential source of environmental contamination. The inclusion of metals such as rare-earth elements offer a possible incentive towards waste valorization if the metals can be extracted and recovered in an economical manner. Rare-earth elements (REEs) have many technological applications and are critically important in the manufacture of electric vehicles, communication devices, and industrial magnets. However, the global supply of rare-earth elements has faced shortages and price shocks. Current methods for separating and isolating individual rare-earth elements use large amounts of energy and organic solvents, raising concerns over environmental impacts. These factors have led to the investigation of nontraditional sources and separation techniques for these elements. Here, we describe a column-based system that uses a newly developed ligand-associated organosilica sorbent to concentrate and separate rare-earth elements from fly ash leachate. The fly ash used in this study originally contained 0.024 wt% rare-earth elements and the final oxide powder after enrichment contained > 10 wt% rare-earth elements, which is a enrichment of > 400 times. This process requires no additional organic solvents after the sorbent media has been synthesized, offering an alternative to the current standard using solvent extraction for rare-earth element recovery.

42 ENGINEERING↗
DOE OSTI2026

CMPO-Functionalized Silica Sorbents for pH-Tunable Separation and Enrichment of Rare-Earth Elements from Environmental Matrices

Rare-earth elements (REEs) are crucial in many applications, yet mutual separation is challenging due to their similar chemical behavior. Octylphenyl- N,N-diisobutyl carbamoyl methyl phosphine oxide (CMPO) is an organophosphorus ligand originally developed for extracting actinides and lanthanides from spent nuclear fuel. Here, we report a pH-tunable CMPOfunctionalized silica sorbent for selective REE separation from complex aqueous matrices. A CMPO-associated silica gel sorbent was synthesized and characterized by Brunauer−Emmett−Teller (BET) surface area, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm the surface functionalization and binding behavior. Sorbent performance was evaluated by using a synthetic 46- element solution and a real phosphate rock fertilizer leachate. Notably, REEs were successfully eluted with ultrapure water, demonstrating reversible desorption controlled by pH adjustment. Packed-bed column studies increased the REE mass fraction from 3.6% to 64% (20-fold enrichment), with up to 30-fold enrichment of neodymium. The adsorption process follows the Langmuir isotherm behavior and follows pseudo-second-order kinetics. The uptake capacity of 1 μmol of REEs per 4.2 μmol of CMPO supports the formation of a predominantly 4:1 ligand:rare earth element(III) pseudocomplex. These results demonstrate CMPO-functionalized silica as a selective, water-elutable, and low-chemical-input platform for sustainable REE recovery from environmental and industrial sources.

chelating ligands↗
DOE OSTI2025

Melting temperature, emissivity, and thermal conductivity of rare-earth silicates for thermal and environmental barrier coatings

In recent years, rare-earth silicates have become the industry standard for coating state-of-the-art SiC ceramic matrix composite (CMC) gas turbine engine components, due to their low volatility, high melting point, and thermal shock resistance. Current research is focused on designing rare-earth silicate based thermal-environmental barrier coatings (T/EBCs) with improved resistance to CMAS (CaO-MgO-Al 2 O 3 -SiO 2 ), steam, and crack formation, while maintaining high temperature performance and stability. Here, in this work we compare the high temperature performance of a variety of single and multi-component rare-earth mono- and disilicates (MS, DS) and rare earth apatites by measuring their melting points and spectrally averaged visible emissivities using laser heating and radiation pyrometry. We also report room temperature thermal conductivity measured by time-domain thermoreflectance (TDTR).

Environmental barrier coatings↗
DOE OSTI2023

Removal of Iron from Pyrite-Rich Coal Refuse by Calcination and Magnetic Separation for Hydrometallurgical Extraction of Rare Earth Elements

In the metallurgical extraction of rare earth elements (REEs), the ratio of contaminant ions to REEs in the leachate dictates the cost and operational efficiency of the downstream processes. The current study investigated the potential iron contamination removal from the feed to the hydrometallurgical process by calcination followed by magnetic separation. The 2.20 specific gravity sink fraction of Baker coal seam coarse refuse was pulverized to finer than 180 μm, calcined at various temperatures, and separated into magnetic and non-magnetic fractions using a wet high-intensity magnetic separator at different field strengths. The untreated feed, calcined products, and their subsequent magnetic and non-magnetic fractions were subjected to acid leaching tests with 1.2 M sulfuric acid at 75 °C and 1% w/v solids concentration. The recovery of light and heavy rare earth elements (LREEs and HREEs, respectively) along with the concentration of common contaminant ions (Al, Ca, and Fe) were measured as output variables. The weight percent of magnetic material was maximized at approximately 29% by calcination at a temperature of 400 °C. Magnetic removal of this fraction using a field strength of 1.15 Tesla resulted in the rejection of 81% of the iron. Leaching of the magnetic fraction provided significantly higher Fe recovery relative to untreated feed material and the non-magnetic fraction. The non-magnetic fraction was subsequently calcined at 600 °C to dehydroxylate the clays and released the REE minerals in the same manner as the treatment of the original coarse refuse material. A comparison of the leachate elemental concentrations resulting from the leaching of both the calcined non-magnetic and original coarse refuse showed only a slight reduction in the iron content from the non-magnetic material. This finding combined with the REE loss in the magnetic fraction resulted in the conclusion that the magnetic removal step was unfavorable.

58 GEOSCIENCES↗
DOE OSTI2020

Methods for liquid extraction of rare earth metals using ionic liquids

A method for extracting a rare earth element from a rare earth-containing substance, the method comprising mixing the rare earth-containing substance with a protic ionic liquid, such as: wherein R1 is selected from hydrogen atom and hydrocarbon groups containing 1 to 6 carbon atoms; R2 and R3 are independently selected from hydrocarbon groups containing 1 to 12 carbon atoms; and X− is an anionic species; to produce a composition of the formula (RE)(amide)yXz at least partially dissolved in the protic ionic liquid, wherein RE is at least one rare earth element having an atomic number selected from 39, 57-71, and 90-103; y is 2-6; z is a number that charge balances the total positive charge of RE; and the amide is the conjugate base of the cationic portion of the protic ionic liquid of Formula (1) and has the following formula:

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

Rare Earth Element—Aluminum Alloys

An alloy includes aluminum, a rare earth element, and an alloying element selected from the following: Si, Cu, Mg, Fe, Ti, Zn, Zr, Mn, Ni, Sr, B, Ca, and a combination thereof. The aluminum (Al), the rare earth element (RE), and the alloying element are characterized by forming at least one form of an intermetallic compound. An amount of the rare earth element in the alloy is in a range of about 1 wt. % to about 12 wt. %, and an amount of the alloying element in the alloy is greater than an amount of the alloying element present in the intermetallic compound.

Moore, Emily E.↗
NASA NTRS1999

Rare Earth Doped High Temperature Ceramic Selective Emitters

As a result of their electron structure, rare earth ions in crystals at high temperature emit radiation in several narrow bands rather than in a continuous blackbody manner. This study develops a spectral emittance model for films of rare earth containing materials. Although there are several possible rare earth doped high temperature materials, this study was confined to rare earth aluminum garnets. Good agreement between experimental and theoretical spectral emittances was found for erbium, thulium and erbium-holmium aluminum garnets. Spectral emittances of these films are sensitive to temperature differences across the film. Emitter efficiency is also a sensitive function of temperature. For thulium aluminum garnet the efficiency is 0.38 at 1700 K but only 0.19 at 1262 K.

Chubb, Donald L.↗
DOE OSTI2024

Alloying effect of rare-earth tritellurides on the charge density wave and magnetic properties

Among many van der Waals materials rare-earth tritellurides (RTe3) allow studying several phenomena like magnetic, superconducting, and charge density wave (CDW). These studies show the effect of cationic alloying of antiferromagnetic RTe3 for fully tunable near room-temperature CDW properties. DyxGd1−xTe3 and DyxTb1−xTe3 alloys were synthesized through a chemical vapor transport technique, and the rare-earth element composition was controlled by changing the ratio of rare-earth metal reagents. The results show that the lattice parameters can be continuously tuned with the composition of the rare-earth cations leading to the variation of the internal chemical pressure. Temperature-dependent Raman spectroscopy and electric transport measurement show that the CDW transition temperature (TCDW) of RTe3 alloys varies with lattice parameters/chemical pressure spanning across 300–380 K. Additional magnetism studies offer the first insights into the magnetic ordering in RTe3 alloys. The emergence of multiple magnetic transitions implies complex magnetic interactions that arise from interactions between different rare-earth elements. Overall findings introduce ways to control the CDW behavior and provide valuable insights into the magnetic ordering in RTe3 alloys, contributing to further investigation and a better understanding of their properties.

Physics↗
DOE OSTI2024

Realignment and suppression of charge density waves in the rare-earth tritellurides 𝑅⁢Te 3 (𝑅 = La, Gd, Er)

The rare-earth tritellurides have a rich phase diagram that includes charge density waves (CDWs), superconductivity, and magnetic order, offering a platform to study the interplay between these phases on a square-net system. Prior studies have shown that defects can affect the CDW characteristics in these materials, yet coupling between the CDW order and the underlying microstructure has not been studied at the nanoscale. Here we use scanning transmission electron microscopy at cryogenic temperatures to directly visualize the effects of defects on the CDW order and provide a spatially resolved microscopic correlation between the CDW transition and structural defects. Here, we show that in the presence of extended defects, such as dislocations and stacking faults, the weak orthorhombicity of the rare-earth tritellurides is lost and the material becomes pseudotetragonal. Since the orthorhombicity acts as a symmetry breaking field for the CDW transitions in rare-earth tritellurides, the presence of these extended defects modulates the energetics of the CDWs and suppresses the ground-state CDW phase at low temperature.

Charge density waves↗
DOE OSTI2022

Ligand-Assisted Separation of Rare Earth Elements via Capillary Electrophoresis

Rare earth elements (REEs) are a class of critical materials vital in applications such as EVs, batteries, and defense weapons systems. These elements are found primarily in ores, and due to their similar chemical behavior, the challenge remains to find an effective means of separation. The addition of ligands of varying charge, size, denticity, etc. can help to increase separation, yet the mechanistic behavior and factors influencing separation are still poorly understood. Here, iminodiacetic acid (IDA) is used to exploit and maximize differences in electrophoretic mobilities between adjacent REEs. Mobilities and diffusion coefficients of REEs in aqueous media are measured via CE and are compared to MD and FEM simulations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Rare Earth Nickelate Electrodes Containing Heavily Doped Ceria for Reversible Solid Oxide Fuel Cells

The electrochemical performance of composite rare-earth nickelate-rare-earth doped ceria oxygen electrodes, with a high level of rare-earth doping in ceria are reported. Additionally, the chemical stability of these compositions is reported at both the sintering (1240 ?C) and operating temperature (800 ?C). Specifically, a lanthanum nickelate La2NiO4+d (LNO) ?? 50 mol% lanthanum doped ceria (LDC50) oxygen electrode and a neodymium nickelate Nd2NiO4+d (NNO) ?? 50 mol% neodymium doped ceria (NDC50) oxygen electrode are tested in solid oxide fuel cell (SOFC) and solid oxide electrolysis cell (SOEC) modes and compared to a composite (La0.75Sr0.25)0.95MnO3±d (LSM)-8 mol% yttria stabilized zirconia (YSZ) electrode. The LNO–LDC50 oxygen electrode reaches a current density which is approximately three times that of the LSM-YSZ electrode in SOFC mode at 0.7 V and approximately two times the LSM-YSZ electrode at 1.2 V in SOEC mode. Similarly the NNONDC50 oxygen electrode reaches a current density which is approximately two times and approximately one and a half times that of LSM-YSZ at 0.7 V and 1.2 V respectively. Oxygen surface exchange results for LNO and NNO are also reported which show different oxygen exchange kinetics during oxidation versus reduction steps.

solid oxide electrolysis, solid oxide fuel cell (S↗
DOE OSTI2025

Adsorption of Rare Earth Elements to Kaolinite [dataset]

Rare earth elements (REEs) are critical components of modern technology behind renewable energy, transportation, and electronics but have a limited current supply. A substantial portion of global REE production relies on ion adsorption deposits. A high abundance of kaolinite in REE enrichment zones within these deposits suggests that kaolinite controls the subsurface migration of REEs. This study aimed to improve the current understanding of REE binding to kaolinite under varying water chemistry conditions. We conducted batch experiments with kaolinite (KGa-2) and three REEs (Nd, Dy, and Yb) at varying pH, electrolyte concentration, dissolved inorganic carbon (DIC), low molecular weight organic acids (citric and oxalic acids), and total REE concentration conditions. Increasing electrolyte concentration inhibits REE adsorption at pH 7, suggesting that ion exchange contributes to adsorption at these pH values. DIC affects adsorption above pH 7−8 by forming strong aqueous complexes with heavy REEs. Citric acid decreases REE adsorption via aqueous complexation of REEs at pH 5 but does not affect adsorption at pH 5. The surface complexation model captures the main adsorption trends with two mechanisms: ion exchange on basal planes at pH ∼6 and inner-sphere surface complexation to edge sites at pH ∼6. Equilibrium constants for surface complexation increase in the order of Yb Dy Nd, indicating a higher strength of adsorption for heavy REEs. This study demonstrates how water chemistry conditions control the adsorption mechanisms that may determine the mobility of REEs in subsurface environments rich in kaolinite.

58 GEOSCIENCES↗
DOE OSTI2021

Influence of the Anionic Zinc-Adeninate Metal–Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams

Rare earth elements (REEs) are critical to numerous technologies; however, a combination of increasing demand, environmental concerns, and monopolistic marketplace conditions has spurred interest in boosting the domestic REE production from sources such as coal utilization byproducts. The economic viability of this approach requires rapid, inexpensive, and sensitive analytical techniques capable of characterizing the REE content during resource exploration and downstream REE processing (e.g., analyzing REE separation, concentration, and purification production steps). Luminescence-based sensors are attractive because many REEs may be sensitized to produce element-specific emission. Hence, a single material may simultaneously detect and distinguish multiple REEs. Metal–organic frameworks (MOFs) can sensitize multiple REEs, but their viability has been hindered by sensitivity and selectivity challenges. Understanding how the MOF structure impacts the REE sensing efficacy is critical to the rational design of new sensors. Here, we evaluate the sensing performance of seven different anionic zinc-adeninate MOFs with different organic linkers and/or structures for the visible-emitting REEs Tb, Dy, Sm, and Eu. The choice of a linker determines which REEs are sensitized and significantly influences their sensitivity and selectivity against competing species (here, Fe(II) and HCl). For a given linker, structural changes to the MOF can further fine-tune the performance. The MOFs produce some of the lowest detection limits (sub-10 ppb for Tb) reported for the aqueous sensitization-based REE detection. Importantly, the most selective MOFs demonstrated the ability to sensitize the REE signal at sub-ppm levels in a REE-spiked acid mine drainage matrix, highlighting their potential for use in real-world sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Technology Development and Integration for Volume Production of High Purity Rare Earth Metals from Phosphate Processing

Under this project and in collaboration with Pacific Northwest National Laboratory (PNNL), Oak Ridge National Laboratory (ORNL), Florida International University (FIU), and Mosaic, the FIPR Institute successfully developed and demonstrated on laboratory batch scale a complete processing technology for production of high-purity rare earth elements (REE) in the form of mixed rare earth oxides (MREO) and rare earth metals (REM) using phosphoric acid sludge (a byproduct from phosphate mining) as the REE feedstock. Based on the research results, a technical research plan has been developed with expanded team members to elevate the technology readiness level (TRL) of the subject technology from 4 to 6 by conducting continuous testing of the processing flowsheet with the ultimate goal of producing about 900 tons per year of REM using the phosphate mining byproduct. Those 900 tons of REM would contain approximately 180 tons of Y, 120 tons of Nd, 50 tons of Gd, 37 tons of Dy, 33 tons of Sm, and 31 tons of Pr, meeting the US demand of roughly 39%, 6%, 42%, 48%, 101% and 7% for these elements, respectively. The advanced technologies for REE separation and purification involves three technology companies: K-Technologies, Inc. would test their continuous-ion-exchange/continuous-ion chromatography technologies on both the REE leachate and solvent extraction concentrate for 4 production of high-purity individual or binary REM. Rare Earth Salts would test their innovative electrochemical technology on the REE leachate or re-dissolved MREO in dilute acid for production of high-purity individual or binary REM. Rare Earth Technologies, Inc. would evaluate their advanced chromatographic separation technology on the dissolved MREO product for production of high-purity individual or binary REM.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Separation of thorium, uranium, and rare earths from a strip solution generated from coarse coal refuse

This work systematically evaluated the separation performance of thorium, uranium, and rare earths when coal and coal byproduct were utilized as a non-traditional feedstock for rare earth production. A synthetic solution was prepared following the elemental composition of a strip solution generated from coarse coal refuse and used throughout the study. Various separation techniques including selective precipitation, solvent extraction, and a modified experimental protocol incorporating the two were applied to extract rare earths while minimizing the non-selective recovery of thorium and uranium into the product stream. Test results indicate that selective precipitation was effective for the removal of thorium at a pH value approaching 5 while solvent extraction preferentially removed uranium from rare earths. Therefore, a modified experimental protocol consisting of both selective precipitation and solvent extraction was subsequently developed and implemented. The findings following the modified experimental protocol indicate that extractant concentration, solvent extraction feed pH, and organic to aqueous (O/A) ratio all played a significant role in the removal of uranium. Among all the tests conducted, the best separation performance was achieved using a one-stage precipitation at a pH value of 4.8, 50 v% TBP, solvent extraction feed pH of 3.5, and an O/A ratio of 3, which corresponded to an overall rare earth, thorium, and uranium recovery of 79.6%, 0%, and 3.1%, respectively.

01 COAL, LIGNITE, AND PEAT↗