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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Quantum paramagnetism in a non-Kramers rare-earth oxide: Monoclinic Pr 2 Ti 2 O 7

Little is so far known about the magnetism of the A 2 B 2 O 7 monoclinic layered perovskites that replace the spin-ice supporting pyrochlore structure for r A /r B > 1.78. We show that high quality monoclinic Pr 2 Ti 2 O 7 single crystals with a three-dimensional network of non-Kramers Pr 3+ ions that interact through edge-sharing superexchange interactions, form a singlet ground-state quantum paramagnet that does not undergo any magnetic phase transitions down to, at least, 1.8 K. The chemical phase stability, structure, and magnetic properties of the layered perovskite Pr 2 Ti 2 O 7 were investigated using x-ray diffraction, transmission electron microscopy, and magnetization measurements. Synthesis of polycrystalline samples with the nominal compositions of Pr 2 Ti 2+x O 7 (–0.16 ≤ x ≤ 0.16 ) showed that deviations from the Pr 2 Ti 2 O 7 stoichiometry lead to secondary phases of related structures including the perovskite phase Pr 2/3 TiO 3 and the orthorhombic phases Pr 4 Ti 9 O 24 and Pr 2 TiO 5 . No indications of site disordering (stuffing and antistuffing) or vacancy defects were observed in the Pr 2 Ti 2 O 7 majority phase. A procedure for growth of high-structural-quality stoichiometric single crystals of Pr 2 Ti 2 O 7 by the traveling solvent floating zone method is reported. Thermomagnetic measurements of single-crystalline Pr 2 Ti 2 O 7 reveal an isolated singlet ground state that we associate with the low-symmetry crystal electric-field environments that split the (2J + 1 = 9)-fold degenerate spin-orbital multiplets of the four differently coordinated Pr 3+ ions into 36 isolated singlets resulting in an anisotropic temperature-independent van Vleck susceptibility at low T. Here, a small isotropic Curie term is associated with 0.96(2)% noninteracting Pr 4+ impurities.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular-level understanding of metal ion retention in clay-rich materials

Clay minerals retain or adsorb metal ions in the Earth’s critical zone. Rocks, sediments and soils rich in clay minerals can concentrate rare earth elements (REEs) in ion adsorption-type deposits (IADs) and are similarly effective at metallic contaminant remediation. However, the molecular-scale chemical and physical mechanisms of metal ion retention remain only partly understood. Here, we describe the nature, location and energy requirements of metal retention at clay mineral surfaces. Retention originates mainly from electrostatic interactions during cation exchange at low pH and chemical bonding in surface complexation and precipitation at neutral and high pH. Surface complexation can induce surface redox reactions and precipitation mechanisms including neoformation of clay mineral layered structures. In IADs, outer-sphere adsorption is the major retention mechanism of REE ions. By contrast, the use of clay minerals in pollution control relies on various mechanisms that can coexist, including cation exchange, surface complexation and nucleation growth. To more effectively leverage clay mineral–metal interactions in resource recovery and contaminant remediation, complex mechanisms such as surface precipitation and redox reactions must be better understood; for instance, by utilizing advances in quantum mechanical calculations, close combination between synchrotron and simulation techniques, and upscaling of molecular-level information in macroscopic thermokinetic predictive models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Epitaxial PbGeSe thin films and their photoluminescence in the mid-wave infrared

PbSe is a narrow bandgap IV–VI compound semiconductor with application in mid-wave infrared optoelectronics, thermoelectrics, and quantum devices. Alkaline-earth or rare-earth elements such as Sr and Eu can substitute Pb to widen the bandgap of PbSe in heterostructure devices, but they come with challenges such as deteriorating optical and electronic properties, even in dilute concentrations due to their dissimilar atomic nature. We substitute Pb instead with column IV Ge and assess the potential of rocksalt phase PbGeSe as a wider bandgap semiconductor in thin films grown by molecular beam epitaxy on GaAs substrates. Low sticking of GeSe adatoms requires synthesis temperatures below 260 °C to incorporate Ge, but this yields poor structural and compositional uniformity as determined by x-ray diffraction. Consequently, as-grown films in the range Pb0.94Ge0.06Se–Pb0.83Ge0.17Se (6%–17% Ge) show much less bandgap widening in photoluminescence than prior work on bulk crystals using absorption. We observe that post-growth rapid thermal annealing at temperatures of 375–450 °C improves the crystal quality and recovers bandgap widening. Rapid interdiffusion of Ge during annealing, however, remains a challenge in harnessing such PbGeSe materials for compositionally sharp heterostructures. Annealed 17% Ge films emit light at 3–3.1 μm with a minimal shift in wavelength vs temperature. These samples are wider in bandgap than PbSe films by 55 meV at room temperature, and the widening increases to 160 meV at 80 K, thanks to sharply different dependence of bandgap on temperature in PbSe vs PbGeSe.

Xiao, Kelly (ORCID:0000000321000838)↗
DOE OSTI2024

Manufacturing and Additive Design of Electric Machines by 3D Printing (MADE3D) (Final Technical Report)

As the U.S clean energy transition hinges on the growth of offshore wind, this is expected to be a major driver for innovations in manufacturing, material and design advancements to enable robust and cost-competitive wind turbines. The race to build larger and taller turbines rated 10 megawatts (MW) and beyond, has intensified pressure on OEMs in terms of logistics of handling and transporting large wind components, securing critical raw material as well as scaling up necessary domestic production infrastructure to meet the demand. There is increased interest in building lightweight, more efficient, and high-power dense drivetrains that will ease the burden on installation, minimize the raw material demand, increasing domestic sourceability. Despite good efficiency and reliability, existing drivetrain technologies such as direct-drive permanent magnet generators are heavy (> 300 tons), expensive, and often rely on large quantities of rare-earth permanent magnets (PMs), steel and copper.

17 WIND ENERGY↗
DOE OSTI2022

Erbium-implanted materials for quantum communication applications

Erbium-doped materials can serve as spin-photon interfaces with optical transitions in the telecom C band, making them an exciting class of materials for long-distance quantum communication. However, the spin and optical coherence times of Er 3+ ions are limited by currently available host materials, motivating the development of new Er 3+ -containing materials. Here we demonstrate the use of ion implantation to efficiently screen prospective host candidates, and show that disorder introduced by ion implantation can be mitigated through post-implantation thermal processing to achieve inhomogeneous linewidths comparable to bulk linewidths in as-grown samples. We present optical spectroscopy data for each host material, which allows us to determine the level structure of each site, allowing us to compare the environments of Er 3+ introduced via implantation and via doping during growth. Here, we demonstrate that implantation can generate a range of local environments for Er 3+ , including those observed in bulk-doped materials, and that the populations of these sites can be controlled with thermal processing.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Improvements to the Powder Processing of near-Final Shape alnico Magnets

Alnico permanent magnets (PMs), a recent PM system of interest as an attractive rare earth-free PM alternative, have advantageous high operating temperature and magnetic saturation with the potential for utilization in electric machines, e.g. interior-PM motors found in electric vehicles, if current directional solidification methods can be replaced by a true mass production approach. Recently, two unique alnico compositions, termed Full-Co and Co-lean, with improved coercivity, were gas atomized, compression molded, and vacuum sintered (4h at 1240°C) to high densities of 97.8% and 99.3%, respectively. However, the Co-lean remained fine grained isotropic magnets and the Full-Co grains were not textured, lowering magnetic strength in spite of attempts to grow large textured grains by a stress-biased solid state grain alignment method to convert them to high energy anisotropic magnets. It was hypothesized that oxidation during de-binding in air left many prior particle boundary oxides within the sintered microstructure that hindered grain growth and texturing during the stress-biased texturing procedure and prevented the desired abnormal grain growth (AGG). Here we explored a vacuum de-binding step that was linked (in-place) to vacuum sintering and found that the Co-lean exhibited faster uniform grain growth that doubled the average grain size (40 μm to 80 μm). Linked vacuum de-binding and sintering of Full-Co produced some AGG after only 1 h of 1240°C sintering. A new direction for promoting AGG (and stress-biased texturing) in alnico is being explored that utilizes a fundamental analysis of systems with second phase particles that either inhibit or boost grain growth. This effort explores the influence of vacuum de-binding linked to a series of lower sintering temperatures at a fixed time (4h) to see if oxide particle size and volume fraction can be changed to promote AGG conditions in alnico. Surprising qualitative results indicate that AGG may be promoted for vacuum sintering at less than 1200°C.

Rinko, Emily↗
DOE OSTI2025

The genome of the polyextremophilic yeast, Naganishia friedmannii, reveals adaptations involved in stress response pathways, carbohydrate metabolism expansion, and a limited DNA repair repertoire

Here we report the draft genome sequence of Naganishia friedmannii (formerly Cryptococcus friedmannii) isolate, a Basidiomycota yeast commonly found in some of the most extreme environments of the Earth's cryosphere. We isolated N. friedmannii strain Llullensis from soils at 6000 m above sea level on Volcán Llullaillaco, Argentina. The genome was 22.2 Mb with 6251 identified protein coding genes. Proteins known to be associated with thermal, osmotic, and radiation stress were identified in the genome. Comparative analysis with seven other Naganishia genomes revealed unique features underlying its polyextremophilic lifestyle. Naganishia friedmannii showed an expansion of genes involved in breaking down plant-derived carbohydrates, supporting the hypothesis that it survives at high elevations by metabolizing wind-deposited organic matter. Surprisingly, many genes involved in cell-cycle checkpoints and DNA repair were missing, as in several other Naganishia species. This extensive loss may be adaptive in extreme environments prone to abiotic stress, where a high mutation rate could generate advantageous traits, and reduced cell-cycle control may allow for faster reproduction that would be advantageous for rapid growth during brief periods of soil wetting following rare snow events.

Vimercati, Lara↗
DOE OSTI2021

Kinetically Controlled Linker Binding in Rare Earth-2,5-Dihydroxyterepthalic Acid Metal–Organic Frameworks and Its Predicted Effects on Acid Gas Adsorption

In the pursuit of highly stable and selective metal–organic frameworks (MOFs) for the adsorption of caustic acid gas species, an entire series of rare earth MOFs have been explored. Each of the MOFs in this series (RE-DOBDC; RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; DOBDC = 2,5-dihydroxyterepthalic acid) was synthesized in the tetragonal space group I4/m. Crystallized MOF samples, specifically Eu-DOBDC, were seen to have a combination of monodentate and bidentate binding when synthesized under typical reaction conditions, resulting in a contortion of the structure. However, extended crystallization times determined that this binding is kinetically controlled and that the monodentate binding option was crystallographically eliminated by extended reaction times at higher temperatures. Furthermore, this series allows for the direct study of the effect of the metal center on the structure of the of the MOF; herein, the lanthanide metal ionic radii contraction across the periodic table results in a reduction of the MOF pore size and lattice parameters. Scanning electron microscopy–energy-dispersive spectroscopy was used to investigate the stages of crystal growth for these RE-DOBDC MOFs. All MOFs, except Er-DOBDC had a minimum of two stages of growth. These analogues were demonstrated by analysis of neutron diffraction (PND) to exhibit a cooperative rotational distortion of the secondary building unit, resulting in two crystallographically distinct linker sublattices. Computational modeling efforts were used to show distinct differences on acid gas (NO 2 and SO 2 ) binding energies for RE-DOBDC MOFs when comparing the monodentate/bidentate combined linker with the bidentate-only linker crystal structures.

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

Quasi-deterministic localization of Er emitters in thin film TiO 2 through submicron-scale crystalline phase control

With their shielded 4f orbitals, rare-earth ions (REIs) offer optical and electron spin transitions with good coherence properties even when embedded in a host crystal matrix, highlighting their utility as promising quantum emitters and memories for quantum information processing. Among REIs, trivalent erbium (Er 3+ ) uniquely has an optical transition in the telecom C-band, ideal for transmission over optical fibers, making it well suited for applications in quantum communication. The deployment of Er 3+ emitters into a thin film TiO 2 platform has been a promising step toward scalable integration; however, like many solid-state systems, the deterministic spatial placement of quantum emitters remains an open challenge. Here, we investigate laser annealing as a means to locally tune the optical resonance of Er 3+ emitters in TiO 2 thin films on Si. Using both nanoscale x-ray diffraction measurements and cryogenic photoluminescence spectroscopy, we show that tightly focused below-gap laser annealing can induce anatase to rutile phase transitions in a nearly diffraction-limited area of the films and improve local crystallinity through grain growth. As a percentage of Er:TiO 2 is converted to rutile, the Er 3+ optical transition blueshifts by 13 nm. We explore the effects of changing laser annealing time and show that the amount of optically active Er:rutile increases linearly with laser power. We additionally demonstrate local phase conversion on microfabricated Si structures, which holds significance for quantum photonics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Extraction, Separation, and Production of High Purity Rare Earth Elements and Critical Minerals from Coal-Based and Related Resources

The general objectives of this project are to develop concepts for rare earth metal and critical mineral production from coal-based and related (minerals associated with coal) resources and incorporate them into a Technical Research Plan with an associated overall flow sheet. The project team has extensive expertise in market evaluation, mineral separation, leaching, chemical separations, alternative metallothermic reaction technology, electrowinning, and electrorefining that was critical to the success of the proposed project. The project included critical industrial partners needed for project success. The project team has extensive expertise in market evaluation, mineral separation, leaching, chemical separations, alternative reduction technology, electrowinning, and electrorefining as well as appropriate pilot-scale facilities to enable this project. The project encompassed broader opportunities for developing domestic resources of REE/CM materials for a more resilient, diverse, and secure supply chain for REE/CM materials with built-in redundancies and appropriate resource stockpiles. The production of REE/CM materials will help to revitalize and rebuild world-class American manufacturing capacity and the related workforce through new jobs and infrastructure. Furthermore, due to the nature and location of the production sites, economic growth in diverse communities of color and economically distressed areas will be cultivated. Finally, this technology can be applied to reuse and remediate coal waste tailings for REE/CM production.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Luminescence of alkali rare earth borates A 3 Ln(BO 3 ) 2 (A = Na, K; Ln = Eu, Tb)

Single crystals of a series of rare earth borates, A 3 Ln (BO 3 ) (A = Na, K; Ln = Eu, Tb), were synthesized using a boric acid/hydroxide melt. The Na 3 Ln (BO 3 ) 2 borates crystallized in the monoclinic system with space group P2 1 /n, and the K 3 Ln (BO 3 ) 2 borates crystallized in the orthorhombic system with space group Pnma. Here, the luminescence of these borates was investigated under ultraviolet and X-ray excitations for the first time. Radioluminescence (RL) measurements showed K 3 Tb(BO 3 ) 2 to be the brightest compound, with an integral intensity equal to 55% of the integral emission of Bi 4 Ge 3 O 12 (BGO) powder.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Optical and microstructural studies of erbium-doped TiO 2 thin films on silicon, SrTiO 3 , and sapphire

Rare-earth ion doped oxide thin films integrated on silicon substrates provide a route toward scalable, chip-scale platforms for quantum coherent devices. Erbium-doped TiO 2 is an attractive candidate: the Er 3+ optical transition is compatible with C-band optical fiber communications, while TiO 2 is an insulating dielectric compatible with silicon process technology. Through structural and optical studies of Er-doped TiO 2 thin films grown via molecular beam deposition on silicon, SrTiO 3 , and sapphire substrates, we have explored the impact of polycrystallinity and microstructure on the optical properties of the Er emission. Comparing polycrystalline TiO 2 (rutile)/Si with single-crystalline TiO 2 (rutile)/r-sapphire and polycrystalline TiO 2 (anatase)/Si with single-crystalline TiO 2 (anatase)/SrTiO 3 , we observe that the inhomogeneous linewidth (Γ inh ) of the most prominent peak in the Er spectrum (the Y 1 –Z 1 transition, 1520 and 1533 nm in rutile and anatase TiO 2 ) is significantly narrower in the polycrystalline case. This implies a relative insensitivity to extended structural defects and grain boundaries in such films (as opposed to, e.g., point defects). We show that the growth of an undoped, underlying TiO 2 buffer on Si can reduce Γ inh by a factor of 4–5. Expectedly, Γ inh also reduces with decreasing Er concentrations: we observe a ∼2 order of magnitude reduction from ∼1000 ppm Er to ∼10 ppm Er. Γ inh then gets limited to a residual value of ∼5 GHz that is insensitive to further reduction in the Er concentration. Based upon the above results, we argue that the optical properties in these thin films are limited by the presence of high “grown-in” point defect concentrations.

Chemical elements↗
DOE OSTI2021

Isotropic nanocrystalline Sm(Fe,Co) 11.3 Ti 0.7 magnets modified with B and Zr

Rare-earth-lean Sm(Fe,Co,Ti) 12 alloys with the ThMn 12 crystal structure and less than one Ti atom per formula unit have the potential of exceptionally powerful permanent magnets, but all prior attempts to develop high coercivity in bulk alloys, especially coercivity combined with crystallographic texture, have fallen short of the expectations. This study was aimed at improvement of the currently best Sm(Fe,Co,Ti) 12 magnets prepared through melt-spinning which are inherently isotropic. Modifications of the alloys with B and Zr, already demonstrated in earlier studies to be effective separately, have been implemented simultaneously. Here, a systematic study of Sm 1.1-x (Fe,Co) 11.3-y Ti 0.7 B y alloys melt-spun at a tangential speed of 50 m/s and annealed at 600–950 °C allowed for monitoring the continuous evolution of the two consecutive crystal structures, those of the TbCu 7 and ThMn 12 types. Zirconium was found to facilitate the formation of the 1:12 structure at the expense of the 1:7, whereas boron has the opposite effect, at certain concentrations completely suppressing the 1:12. When the two alloying elements are introduced simultaneously, they inhibit growth of the 1:12 crystallites at annealing temperatures higher than 800 °C, thus allowing for the development of a higher coercivity. Because of instrumental limitations, bulk magnets were prepared through a two-step process – compaction of the melt-spun ribbons at 650 °C and additional treatment at a higher temperature – and they were characterized by a reduced, 90–93%, density. Nevertheless, an isotropic Sm 0.9 Zr 0.2 (Fe,Co) 10.8 Ti 0.7 B 0.5 magnet exhibited fair values of the remanence (7.4 kG), maximum energy product (8.5 MGOe) and coercivity (5.4 kOe), as well as high Curie temperature of 525 °C and remarkably small temperature coefficient of the coercivity, -0.25%/°C.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dry air cyclic oxidation of mixed Y/Yb disilicate environmental barrier coatings and bare silica formers

Here mixed Y and Yb disilicate coatings (Y/Yb)DS have been proposed as dual function thermal and environmental barrier coatings (EBCs) for protecting SiC-based ceramic matrix composites in gas-turbine environments. As an initial step, the 1350 °C dry air cyclic oxidation of atmospheric plasma sprayed (Y 1.2 /Yb 0.8 )DS and ytterbium disilicate/ytterbium monosilicate (YbDS/YbMS) EBCs deposited onto Si bond coatings was compared. As a baseline for evaluating EBC oxidant permeability, the dry air cyclic oxidation scale growth rates for bare silica formers (SiC, Si) were also measured and were consistently higher than rates previously measured after isothermal oxidation. Regarding Si bond coat oxidation rates underlying (Y/Yb)DS and YbDS/YbMS EBCs, the thinner silica scale formed under the thinner and denser (Y/Yb)DS coatings suggested a lower oxidant permeability than YbDS/YbMS. After 500 1-h cycles, the (Y/Yb)DS coating was comprised of only the β-polymorph disilicate and minor amounts of the X-2 phase monosilicate phase. Negligible differences in oxidation kinetics for (Y/Yb)DS coatings over the 90 – 240 µm thickness range were observed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Predicting Water Cycle Characteristics from Percolation Theory and Observational Data

The fate of water and water-soluble toxic wastes in the subsurface is of high importance for many scientific and practical applications. Although solute transport is proportional to water flow rates, theoretical and experimental studies show that heavy-tailed (power-law) solute transport distribution can cause chemical transport retardation, prolonging clean-up time-scales greatly. However, no consensus exists as to the physical basis of such transport laws. In percolation theory, the scaling behavior of such transport rarely relates to specific medium characteristics, but strongly to the dimensionality of the connectivity of the flow paths (for example, two- or three-dimensional, as in fractured-porous media or heterogeneous sediments), as well as to the saturation characteristics (i.e., wetting, drying, and entrapped air). In accordance with the proposed relevance of percolation models of solute transport to environmental clean-up, these predictions also prove relevant to transport-limited chemical weathering and soil formation, where the heavy-tailed distributions slow chemical weathering over time. The predictions of percolation theory have been tested in laboratory and field experiments on reactive solute transport, chemical weathering, and soil formation and found accurate. Recently, this theoretical framework has also been applied to the water partitioning at the Earth’s surface between evapotranspiration, ET, and run-off, Q, known as the water balance. A well-known phenomenological model by Budyko addressed the relationship between the ratio of the actual evapotranspiration (ET) and precipitation, ET/P, versus the aridity index, ET 0 /P, with P being the precipitation and ET 0 being the potential evapotranspiration. Existing work was able to predict the global fractions of P represented by Q and ET through an optimization of plant productivity, in which downward water fluxes affect soil depth, and upward fluxes plant growth. In the present work, based likewise on the concepts of percolation theory, we extend Budyko’s model, and address the partitioning of run-off Q into its surface and subsurface components, as well as the contribution of interception to ET. Using various published data sources on the magnitudes of interception and information regarding the partitioning of Q, we address the variability in ET resulting from these processes. The global success of this prediction demonstrated here provides additional support for the universal applicability of percolation theory for solute transport as well as guidance in predicting the component of subsurface run-off, important for predicting natural flow rates through contaminated aquifers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Thermally generated magnonic spin currents in a polycrystalline gadolinium iron garnet thin film with perpendicular magnetic anisotropy

Rare-earth iron garnets (REIGs) are the benchmark systems for magnonics, including the longitudinal spin Seebeck effect (LSSE). While most research has focused on single-crystalline REIGs on complimentary garnet substrates, moving to more, cost-effective complementary metal-oxide semiconductor (CMOS)-compatible substrates is important to integrate REIG thin films with existing technology. In this regard, we grow a 130 nm-thick polycrystalline gadolinium iron garnet (GdIG) film on the Si/SiO2 substrate and investigate the temperature-dependent LSSE. Interestingly, the polycrystalline GdIG film exhibits perpendicular magnetic anisotropy (PMA) at room temperature which is induced by tensile in-plane (IP)-strain originating from the thermal-expansion mismatch between the GdIG film and the substrate during rapid thermal annealing. Further, a spin-reorientation transition from the out-of-plane IP direction below TS = 180 K is observed. Additionally, the film reveals a magnetic compensation temperature, TComp, of ≈240 K. The LSSE voltage not only demonstrates a sign-inversion around TComp, but also shows noticeable changes around TS. As compared to a single-crystalline GdIG film, the lower LSSE voltage for the polycrystalline GdIG is attributed to the higher effective magnetic anisotropy and enhanced magnon scattering at the grain boundaries. Our study not only paves the way for the cost-effective growth of CMOS-compatible REIG-based systems with PMA for magnonic memory and information processing applications, but also highlights the fact that the spincaloritronic and spin-insulatronic properties of the polycrystalline REIGs follow those of their single-crystalline counterparts with reduced spin-to-charge conversion efficiency through LSSE which can be tuned further by controlling the average gran size and interface engineering.

Physics↗
DOE OSTI2024

Intricate Magnetic Landscape in Antiferromagnetic Kagome Metal TbTi 3 Bi 4 and Interplay with Ln 2– x Ti 6+ x Bi 9 (Ln: Tb···Lu) Shurikagome Metals

Here we present the discovery and characterization of the kagome metal TbTi 3 Bi 4 in tandem with a new series of compounds, the Ln 2–x Ti 6+x Bi 9 (Ln: Tb–Lu) shurikagome metals. We previously reported on the growth of the LnTi 3 Bi 4 (Ln: La–Gd 3+ , Eu 2+ , Yb 2+ ) family, a chemically diverse and exfoliable series of kagome metals with complex and highly anisotropic magnetism. However, unlike the La–Gd analogs, TbTi 3 Bi 4 cannot be synthesized by our previous methodology due to phase competition with crystals of Ln 2–x Ti 6+x Bi 9 (x ~ 1.7–1.2). Here we discuss the phase competition between the LnTi 3 Bi 4 and Ln 2–x Ti 6+x Bi 9 families, helping to frame the difficulty in synthesizing LnTi 3 Bi 4 compounds with small Ln species and providing a strategy to circumvent the formation of Ln 2–x Ti 6+x Bi 9 . Detailed characterization of the magnetic and electronic transport properties on single crystals of TbTi 3 Bi 4 reveals a highly complex landscape of magnetic phases arising from an antiferromagnetic ground state. A series of metamagnetic transitions creates at least 5 unique magnetic phase pockets, including a 1/3 and 2/3 magnetization plateau. Further, the system exhibits an intimate connection between the magnetism and magnetotransport, exhibiting sharp switching from positive (+40%) to negative magnetoresistance (–50%). Like the LnTi 3 Bi 4 kagome metals, the Ln 2–x Ti 6+x Bi 9 family exhibits quasi-2D networks of titanium and chains of rare earth. Finally, we present the structures and some basic magnetic properties of the Ln 2–x Ti 6+x Bi 9 family alongside our characterization of the newly discovered TbTi 3 Bi 4 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗