Search NASA⌕ Search

SEARCH · Search NASA

Results for “zirconates”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 271 records · Page 15

Neodymium and lead isotope evidence for enriched early Archean crust in North America

Neodymium and lead isotope measurements and uranium-lead zircon geochronology from Archaean gneisses of the Slave Province in the Northwest Territories of Canada are reported. The gneisses contain zircons with cores older than 3.842 Gyr and an epsilon(Nd) (3.7 Gyr) of - 4.8. This is the oldest reported chondritic model age for a terrestrial sample and provides evidence for strongly enriched pre-3.8-Gyr crust, a reservoir complementary to the depleted mantle already in existence by 3.8 Gyr before the present.

Bowring, Samuel A.↗

Chronology of lunar granite 12033,576: Resetting of Rb-Sr and K-Ca isochrons

Lunar granite 12033,576 is a subsample of the 'large' (approximately 1 g) felsite 12033,507 which was identified from a collection of 4-10 mm particles from the 12033 soil sampled from the north rim of Head Crater in the eastern part of Oceanus Procellarum. Discordant ages of approximately 3.6, approximately 0.8, approximately 3.9, and approximately 2.2 Ga for this lunar granite were obtained, respectively, by the K-Ca, Ar-39/Ar-40, and U-Pb zircon methods in previous studies and by the Rb-Sr method is this study. Assuming the granite crystallized approximately 3.9 Ga ago (zircon age) and was shocked by meteoritic impacts at 0.8 Ga ago (Ar-39-Ar-40 age), the intermediate apparent ages by the Rb-Sr and K-Ca methods can be interpreted as reset by diffusion of the parent and daughter nuclides. The Rb-Sr age is less resistant to resetting than the K-Ca age, but more resistant that the Ar-39/Ar-40 age.

Shih, C.-Y.↗

Calibrating rates of early Cambrian evolution

An explosive episode of biological diversification occurred near the beginning of the Cambrian period. Evolutionary rates in the Cambrian have been difficult to quantify accurately because of a lack of high-precision ages. Currently, uranium-lead zircon geochronology is the most powerful method for dating rocks of Cambrian age. Uranium-lead zircon data from lower Cambrian rocks located in northeast Siberia indicate that the Cambrian period began about 544 million years ago and that its oldest (Manykaian) stage lasted no less than 10 million years. Other data indicate that the Tommotian and Atdabanian stages together lasted only 5 to 10 million years. The resulting compression of Early Cambrian time accentuates the rapidity of both the faunal diversification and subsequent Cambrian turnover.

Bowring, Samuel A.↗

Materials Selection and Their Characteristics as Used in Rapid Prototyping

NASA's Marshall Space Flight Center (MSFC) conducted a program to evaluate six technologies used in Rapid Prototyping (RP) to produce investment casting patterns. In this paper, RP refers to the collective additive fabrication technologies known as Solid Free-Form Fabrication. Such technologies are being used with increasing frequency in manufacturing applications, due in part to their rapidly expanding capabilities to fabricate models from many types of materials. This study used ABS plastic, polycarbonate, TrueForm PM6, epoxy resin, paper, starch, and wax. The baseline model was a semi-complex prototype fuel pump housing, intended for use in the X-33 reusable launch vehicle. All models were shelled in a production- grade colloidal silica ceramic. Primary coats were zircon-base flour with zircon backup, while secondary coats were silica grains with a tabular alumina backup. Each model was shelled in an identical manner, using the same atmospheric conditions and drying times, as well as the same number of layers. Bake-outs and firing cycles were consistent with the leach ability of each material. Preheat and bath temperatures were also kept consistent. All molds were cast in vacuum using a hydrogen-resistant superalloy (NASA- 23) that was developed in-house. The final technical evaluation included detailed measurements of the model and the final casting, in order to determine any dimensional changes caused by different pattern materials, as well as documentation of all defects and any obvious refractory/model reactions. Prototype production costs were estimated for each method and taken into consideration during trade-off analysis.

Cooper, K.↗

Recognition of > or = 3850 Ma water-lain sediments in West Greenland and their significance for the early Archaean Earth

A layered body of amphibolite, banded iron formation (BIF), and ultramafic rocks from the island of Akilia, southern West Greenland, is cut by a quartz-dioritic sheet from which SHRIMP zircon 206Pb/207Pb weighted mean ages of 3865 +/- 11 Ma and 3840 +/- 8 Ma (2 sigma) can be calculated by different approaches. Three other methods of assessing the zircon data yield ages of >3830 Ma. The BIFs are interpreted as water-lain sediments, which with a minimum age of approximately 3850 Ma, are the oldest sediments yet documented. These rocks provide proof that by approximately 3850 Ma (1) there was a hydrosphere, supporting the chemical sedimentation of BIF, and that not all water was stored in hydrous minerals, and (2) that conditions satisfying the stability of liquid water imply surface temperatures were similar to present. Carbon isotope data of graphitic microdomains in apatite from the Akilia island BIF are consistent with a bio-organic origin (Mojzsis et al. 1996), extending the record of life on Earth to >3850 Ma. Life and surface water by approximately 3850 Ma provide constraints on either the energetics or termination of the late meteoritic bombardment event (suggested from the lunar cratering record) on Earth.

NASA Discipline Exobiology↗

The Life and Times of Supervolcanoes: Inferences from Long Valley Caldera

Cataclysmic eruptions of silicic magma from "supervolcanoes" are among the most awe-inspiring natural phenomena found in the geologic record, in terms of size, power, and potential hazard. Based on the repose intervals between eruptions of this magnitude, the magmas responsible for them could accumulate gradually in the shallow crust over time scales that may be in excess of a million years (Smith, 1979; Spera and Crisp, 1981; Shaw, 1985). Pre-eruption magma residence time scales can also be inferred from the age difference between eruption (i.e., using 40Ar/39Ar dating to determine the time when hot erupted material cools to below its Ar closure temperature, 200 to 600 degC) and early pre-eruption crystallization (i.e., zircon saturation temperatures; Reid et al., 1997). I will discuss observations from Long Valley a Quaternary volcanic center in California. Long Valley is a voluminous, dominantly silicic caldera system. Based on extensive dating of accessory minerals (e.g., U-Th-Pb dating of zircon and allanite) along with geochemical and isotopic data we find that silicic magmas begin to crystallize 10's to 100's of thousands of years prior to their eruption and that rhyolites record episodes of punctuated and independent evolution rather than the periodic tapping of a long-lived magma. The more punctuated versus more gradual magma accumulation rates required by the absolute and model ages, respectively, imply important differences in the mass and heat fluxes associated with the generation, differentiation, and storage of voluminous rhyolites and emphasize the need to reconcile the magmatic age differences.

Simon, Justin↗

Sphene Emotional: How Titanite Was Shocked When the Dinosaurs Died

Accessory mineral geochronometers such as zircon, monazite, baddeleyite, and xenotime are increasingly being recognized for their ability to preserve diagnostic microstructural evidence of hypervelocity processes. However, little is known about the response of titanite to shock metamorphism, even though it is a widespread accessory phase and U-Pb geochronometer. Here we report two new mechanical twin modes in titanite within shocked granitoids from the Chicxulub impact structure, Mexico. Titanite grains in the newly acquired International Ocean Discovery Program Site expedition 364 M0077A core preserve multiple sets of polysynthetic twins, most commonly with composition planes (K1), = ~{1̅11}, and shear direction (η1) = <110>, and less commonly with the mode K1 = {130}, η1 = ~<522>. In some grains, {130} deformation bands have formed concurrently with shock twins, indicating dislocation glide with Burgers vector b = [341] can be active at shock conditions. Twinning of titanite in these modes, the presence of planar deformation features in shocked quartz, and lack of diagnostic shock microstructures in zircon in the same samples highlights the utility of titanite as a shock indicator for a shock pressure range between ~12 and ~17 GPa. Given the challenges of identifying ancient impact evidence on Earth and other bodies, microstructural analysis of titanite is here demonstrated to be a new avenue for recognizing impact deformation in materials where other impact evidence may be erased, altered, or did not manifest due to low shock pressure.

Timms, Nicholas E.↗

Applicability of Micro X-Ray Fluorescence Spectroscopy to Astromaterials Curation and Research

Introduction: The Astromaterials Acquisition and Curation Office at NASA’s Johnson Space Center (JSC) curates NASA’s astromaterial sample collections which includes: Apollo samples, Luna samples, Ant-arctic meteorites, cosmic dust particles, microparticle impacts into space-flown materials, Genesis solar wind atoms, Stardust comet Wild-2 particles, Stardust inter-stellar particles, Hayabusa asteroid Itokawa particles, Hayabusa 2 asteroid Ryugu particles, and future OSIRIS-Rex asteroid Bennu particles (landing in Sep-tember, 2023) [1–3]. To enhance JSC’s advanced cu-ration capabilities, we have recently installed a high-performance micro-X-ray fluorescence (µXRF) spec-trometer to assist in sample characterization through rapid, non-destructive, in-situ elemental analyses that do not require the sample preparation protocols (i.e., polishing and carbon-coating) commonly needed for electron beam analyses. With this new instrument, we are capable of detecting all elements down to carbon in a variable-pressure or He-purged chamber for anal-ysis of a wide range of sample types. Here we describe the instrumental set-up, capabilities, and applicability of µXRF analysis to astromaterials curation and re-search. Instrumentation and Methodology: The X-ray fluorescence and computed tomography lab (X-FaCT) lab at JSC is now equipped with a Bruker M4 Tornado Plus µXRF (Fig. 1). This system is an energy-dispersive x-ray spectrometer equipped with two 60 mm2 silicon drift detectors (SDD) that are able to be used simulta-neously for output count rates ~500,000 cps. New light element windows allow detecting and analyzing the entire elemental range from carbon to americium. Two x-ray tubes (micro-focus Rh with polycapillary lenses and W with collimators of 0.5, 1.0, 2.0, and 4.5 mm) with max excitation parameters of 50 kV, 30 W and 50 kV, 40 W, respectively, allow for more flexibility of the analysis of high energy lines. The motorized X-Y-Z stage has a mapping range of 190 x 160 mm and can support samples up to 7 kg (~15.5 lbs) and a height of 120 mm [4]. Analytical modes include elemental analysis (down to ~20 µm spot size) via point, line, or area of bulk materials (rock surfaces, thin sections, thick sections, etc.) as well as coating analysis (determination of thickness and composition) of samples. This system has a variable vacuum chamber (1 mbar to 1 atm) that is also equipped with a He-purge system which accommodates vacuum sensitive samples while still allowing detection of light elements at atmospheric pressure. Utility and Applicability of µXRF in Astro-materials research and exploration science (ARES): Elemental analysis using µXRF is commonly em-ployed for both terrestrial and planetary geological science disciplines [5]. It is especially useful for analy-sis of astromaterials given the limited sample prepara-tion required, which is not feasible for certain materi-als. Here we show select applications of µXRF anal-yses of astromaterials that can, have, and will be done at JSC’s X-FaCT lab. Point analysis: In-situ spot analyses (~20 µm spot size) on a cut slab of Martian meteorite NWA 10922 allowed for the discovery, qualitative elemental analy-sis and determination of different feldspar minerals [6]. These point analyses served as an effective prelim-inary step for subsequent quantitative analyses. Ana-lytical standards can be employed for more accurate quantification of µXRF spot analyses. Area analysis: This analytical mode measures all detectable elements (from C to Am) at each pixel (>5 µm pixel size) in a user-defined area. The results are shown as elemental maps which can be extracted as 16-bit TIFF’s for further data processing. In Fig. 2. we show elemental distribution maps of the high-Ti basalt 73001,531 that have been processed using ImageJ software. From these maps you can accurately and quickly (this map took ~50 mins.) identify mineral components, such as pyroxene, plagioclase, oxides, and phosphates, compositional zoning, and mineral textures. Detection of high-Z phases: µXRF techniques are es-pecially effective at analyzing trace minerals with high-atomic-number (high-Z) elements because the high-energy characteristic X-rays used (relative to SEM EDS) allow for mapping of K lines in elements up to La (typically SEM maps use L X-ray lines for elements >Zn, and these can often have interferences). Thus, µXRF is especially suited for identifying minerals like zircon, baddeleyite, REE-rich phosphates, Fe-rich met-als, oxides, sulfides, and phosphides [4]. In Fig. 3 we show elemental distribution maps for 73001,530 where we are able to correlate the original video image with, Zr, Si, Y and Hf elemental maps together identi-fying the location of a zircon. In this location you would expect lower Si compared to surrounding mate-rial, as well as higher Zr, Y, and Hf content compared to surrounding material, all of which is confirmed by our XRF ele-mental distribution maps (Figure 2.) Conclusions: The new M4 Tornado Plus µXRF within the Astromaterials Acquisition and Curation office at NASA JSC allows for rapid and non-destructive elemental analysis of astromaterials with limited or no sample preparation. µXRF analyses pro-vide crucial compositional knowledge for the prelimi-nary examination and curation of astromaterials. This instrument enhances the advanced curation capabili-ties in the X-FaCT laboratory at JSC by allowing pro-ductive, cohesive, and non-destructive multi-modal x-ray analyses on astromaterial samples, which is neces-sary for the comprehensive curation and study of our current and future astromaterial collections. Addition-ally, µXRF can provide complimentary information to researchers for studies on astromaterials. References: [1] Allen, C. et al., (2011). Chemie De Erde Geochemistry, 71, 1-20. [2] McCubbin, F. M. et al., (2016) 47th LPSC, abstract #2668 [3] Zeigler, R. A. et al., (2017) 48th LPSC, abstract #2772 [4] Bruker User Manual [5] Young et al., (2016) Appl. Geochemistry, 72, 77-87 [6] Mor-ris, R. V. et al., (2023) 54th LPSC.

E W O'Neal↗

Evidence for a ~1 Ga Hypervelocity Impact Event Found in Northwest Greenland

There are likely many undiscovered impact structures on Earth, but several challenges prevent their detection, including possible concealment beneath large ice sheets. In recent years, geophysical, geochemical, and microphysical evidence has mounted for a ca. 58 Ma impact structure under the Hiawatha Glacier, northwest Greenland. Here, we report evidence for a second, much older hypervelocity impact event in this region, recorded in an impact melt rock sample collected from a glaciofluvial deposit in Inglefield Land. Secondary ion mass spectrometry U-Pb analyses of shock metamorphosed zircon grains yielded a previously unrecorded, Proterozoic best estimate impact age of 1039 ± 16 Ma (mean square of weighted deviates = 2.9). Based on Archean−Proterozoic target rock U-Pb ages obtained from unshocked zircon grains and the location of the melt rock sample along the ice margin, we suggest this sample was derived from a hypervelocity impact structure farther inland, concealed by the Greenland Ice Sheet. This study demonstrates the ability to uncover new impact events in some of the most inaccessible areas on Earth and the possibility of sampling multiple impact structures from one location when examining ex situ material. Our results have implications for current and future Martian and lunar returned samples that demonstrably bear complex impact histories.

William R. Hyde↗

DEGRADATION OF SM2ZR2O7 THERMAL BARRIER COATING CAUSED BY CALCIUM-MAGNESIUM-ALUMINUM-SILICON OXIDE (CMAS) DEPOSITION

Rare earth zirconates are promising materials for use as thermal barrier coatings in gas turbine engines. Among the lanthanide zirconate materials, Sm2Zr2O7 with the pyrochlore structure has lower thermal conductivity and better corrosion resistance against calcium-magnesium-aluminum-silicon oxide (CMAS). In this work, after reaction with CMAS, the pyrochlore structure transforms to the cubic fluorite structure and Ca2Sm8(SiO4)6O2 forms in elongated grain.

36 MATERIALS SCIENCE↗

Method for the generation of power

Disclosed herein is a method comprising heating a strontium-containing compound using radiation in a first reactor; decomposing the strontium-containing compound into an oxide and carbon dioxide as a result of heat generated by the exposure to the radiation; reacting the oxide and the carbon dioxide in a second reactor; where the oxide and carbon dioxide react to produce heat; heating a working fluid using the heat produced in the second reactor; and driving a turbine with the heated working fluid to generate energy. Disclosed herein too is a composition comprising strontium carbonate; and strontium zirconate; where the mass ratio of strontium carbonate to strontium zirconate 2:8 to 8:2.

Klausner, James↗

Advanced Characterization of Rare Earth Elements in Coal Utilization Byproducts

Rare earth elements (REE) in various forms (e.g., crystalline mineral phases; adsorbed/absorbed state on and into organic macerals, neoformed glass from flyash or bottom ash) from domestic feedstocks such as coal deposits to coal utilization byproducts (CUB) have the potential to reduce foreign REE dependence and increase domestic resource security. Characterization is critical for understanding environmental risks related to their fate and transport as well as determining the most practical and economical techniques for concentrating the REE and converting them into chemical stocks for manufacturing. Several complementary electron microscopy (SEM-EDS, EPMA-WDS, FIB-SEM, cathodoluminescence, and XRD) and post image processing techniques were used to understand REE transition from coal to CUB. Sites of interest were identified and imaged and respective elemental x-ray maps acquired and montaged. Pixel classification of SEM imagers was completed using image analysis techniques to quantify the distribution of REE associated features. Quantitative elemental analysis of phases were completed using EMPA-WDS followed by FIB-SEM. The FIB-SEM results were reconstructed into 3D volumes and features of interest (e.g. monazite) were analyzed to determine the structure and volumetric estimation of REEs and thus predict detrital REE phases to ICP-MS results. Trace minerals were identified as pyrite, zircon, REE-phosphates' (monazite, xenotime), and barite within the coal tailings. In CUB, amorphous aluminosilicates, iron oxide cenospheres, and calcium oxides were present; monazite appear to be unaltered and unaffected by the combustion process in these samples. Thermal decomposition may have occurred due to presence of detrital zircon and xenotime and subsequent thin Ca-oxide coating enriched in trace REEs.

Verba, Circe↗

Method for the generation of power

Disclosed herein is a method comprising heating a strontium-containing compound using radiation in a first reactor; decomposing the strontium-containing compound into an oxide and carbon dioxide as a result of heat generated by the exposure to the radiation; reacting the oxide and the carbon dioxide in a second reactor; where the oxide and carbon dioxide react to produce heat; heating a working fluid using the heat produced in the second reactor; and driving a turbine with the heated working fluid to generate energy. Disclosed herein too is a composition comprising strontium carbonate; and strontium zirconate; where the mass ratio of strontium carbonate to strontium zirconate 2:8 to 8:2.

Klausner, James F.↗

Rapid pyrolysis to form super ionic conducting lithium garnets

A method of preparing a lithium-ion conducting garnet via low-temperature solid-state synthesis is disclosed. The lithium-ion conducting garnet comprises a substantially phase pure aluminum-doped cubic lithium lanthanum zirconate (Li 7 La 3 Zr 2 O 14 ). The method includes preparing nanoparticles comprising lanthanum zirconate (La 2 Zr 2 O 7 -np) via pyrolysis-mediated reaction of lanthanum nitrate (La(NO 3 ) 3 ) and zirconium nitrate (Zr(NO 3 ) 4 ). The method also includes pyrolyzing a solid-state mixture comprising the La 2 Zr 2 O 7 -np, lithium nitrate (LiNO 3 ), and aluminum nitrate (Al(NO 3 ) 3 ) to give the Li 7 La 3 Zr 2 O 14 and thereby prepare the lithium-ion conducting garnet. A lithium-ion conducting garnet prepared via the method is also disclosed.

Daemen, Luc L.↗

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↗

Local probing of ferroelectric and ferroelastic switching through stress-mediated piezoelectric spectroscopy

The role of local strains is fundamental to the large effective piezoelectric and ferroelectric response of thin films. Therefore a method to investigate local strain-induced phenomena is imperative. Here, pressure induced domain reorganization is reported in lead zirconate titanate films with composition near the morphotropic phase boundary. An approach is thus demonstrated to simultaneously study the role of applied mechanical pressure on multiple local properties of the film. In particular, the modification of hysteresis loops collected at different tip pressures is consistent with first mostly ferroelastic and then ferroelectric dominated reorientation of domains under increasing applied pressure. The pressure induced domain writing is also investigated through phase field simulations where the applied pressure is generally found to increase the in-plane polarization of the domains with respect to the out-of-plane component, corroborating the experimental observations. The approach developed here has the potential to explore other hysteretic phenomena and phase transitions in a spatially resolved manner with varying local pressure.

36 MATERIALS SCIENCE↗

Tunable Microwave Conductance of Nanodomains in Ferroelectric PbZr 0.2 Ti 0.8 O 3 Thin Film

Ferroelectric materials exhibit spontaneous polarization that can be switched by electric field. Beyond traditional applications as nonvolatile capacitive elements, the interplay between polarization and electronic transport in ferroelectric thin films has enabled a path to neuromorphic device applications involving resistive switching. A fundamental challenge, however, is that finite electronic conductivity may introduce considerable power dissipation and perhaps destabilize ferroelectricity itself. In this work, tunable microwave frequency electronic response of domain walls injected into ferroelectric lead zirconate titanate (PbZr 0.2 Ti 0.8 O 3 ) on the level of a single nanodomain is revealed. Tunable microwave response is detected through first-order reversal curve spectroscopy combined with scanning microwave impedance microscopy measurements taken near 3 GHz. Contributions of film interfaces to the measured AC conduction through subtractive milling, where the film exhibited improved conduction properties after removal of surface layers, are investigated. Using statistical analysis and finite element modeling, we inferred that the mechanism of tunable microwave conductance is the variable area of the domain wall in the switching volume. These observations open the possibilities for ferroelectric memristors or volatile resistive switches, localized to several tens of nanometers and operating according to well-defined dynamics under an applied field.

36 MATERIALS SCIENCE↗

Processing and properties of PSZT 95/5 ceramics with varying Ti and Nb substitution

Niobium doped lead-tin-zirconate-titanate ceramics near the PZT 95/5 orthorhombic AFE – rhombohedral FE morphotropic phase boundary Pb 1-0.5y (Zr 0.865-x Ti x Sn 0.135 ) 1-y Nb y O 3 were prepared according to a 2 2+1 factorial design with x = 0.05, 0.07 and y = 0.0155, 0.0195. The ceramics were prepared by a traditional solid-state synthesis route and sintered to near full density at 1250°C for 6 hours. All compositions were ~98% dense with no detectable secondary phases by XRD. The ceramics exhibited equiaxed grains with intergranular porosity and grain size was ~5 μm, decreasing with niobium substitution. Compositions exhibited remnant polarization values of ~32 μC/cm 2 , increasing with Ti substitution. Depolarization by the hydrostatic pressure induced FE-AFE phase transition was drastically affected by variation of the Ti and Nb substitution, increasing at a rate of 113 MPa / 1% Ti and 21 MPa / 1% Nb. Total depolarization output was insensitive to the change in Ti and Nb substitution, ~32.8 μC/cm 2 for the PSZT ceramics. The R3c-R3m and R3m-Pm3m phase transition temperatures on heating ranged from 90 to 105°C and 183 to 191°C, respectively. Ti substitution stabilized the R3c and R3m phases to higher temperatures, while Nb substitution stabilized the Pm3m phase to lower temperatures. Thermal hysteresis of the phase transitions was also observed in the ceramics, with transition temperature on cooling being as much as 10°C lower.

36 MATERIALS SCIENCE↗