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At least 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Advanced Fossil Energy Separations and Analysis Research – Thermal Desorption Using Spouted Beds

Mercury and other contaminants in emissions from coal-fired power plants are of interest due to the cost associated with capture and disposal of toxic mercury species. It had recently been postulated in the fossil energy community that spouted beds may be a viable coal pre-treatment technique for thermal desorption of mercury. Spouted beds have the potential to be a near-ideal solid-gas contactor for desorption of mercury species, especially with a few proposed design changes specific for this application. Introduction of draft tubes for spouted beds has addressed some issues with scale-up to better handle the throughput and particle size found in coal-fired power plants. In Phase I, Mainstream Engineering invented and developed a Venturi draft tube spouted bed (VDTSB) to enable process scale-up with fine coal particles and to improve heat and mass transfer. The VDTSB concept increases suction at the bottom of the bed to better entrain material (and reduce the propensity for bridging) at the bottom of the conical vessel. The main advantages of this patent-pending approach are the ability to accept a wide range of coal particle sizes, good heat/mass transfer, process scalability, and robustness. The desorber design was optimized through bed flow visualization experiments; these experiments demonstrated the increased throughput and ease of process scale-up. A high-temperature pilot-scale VDTSB desorber system was designed, fabricated, commissioned, and tested. The heat and mass transfer rates with the VDTSB were measured and compared to a baseline spouted bed with and without a conventional straight draft tube. Pilot-scale VDTSB system performance tests were completed with the Energy and Environmental Research Center (EERC) to measure the rate of mercury desorption over a range of pulverized coal particle sizes, bed temperatures, and reactor geometry. Based on performance results, an initial technoeconomic analysis (TEA) was completed to estimate the cost reduction for emissions treatment compared to current flue-gas mercury capture systems. The following was accomplished in Phase I: Developed scalable design correlations for high-throughput spouted bed systems; Determined cycle time distribution (CTD) and turnover time for straight and Venturi draft tube spouted beds, and showed the VDTSB had lower cycle time (faster turnover) than the straight draft tube (SDT); Reduced weighted-average turnover time by 14% to 43% with Venturi draft tube; narrowed the CTD by up to 75%; Measured heat and mass transfer within the pilot-scale VDTSB desorber and showed that the highest heat transfer rate was 2.98 kW/m 2 ·s with 400 µm particles at a 10 L/min motive gas flowrate; Measured mercury (Hg) desorption rate for lignite, bituminous, and subbituminous coal at 200 °C, 225 °C, 250 °C and 275 °C; Achieved 5.6×10 -10 kg/m 2 -h, 2.6×10 -10 kg/m 2 -h, and 6.5×10 -11 kg/m 2 -h Hg removal rates for lignite, bituminous, and sub-bituminous coals, respectively with no loss in volatile matter and an increase in heating value due to a reduction in moisture content; The unoptimized VDTSB pilot desorber decreased the total mercury concentration of lignite and bituminous coal tests by 61% (dry basis). The subbituminous Powder River Basin (PRB) coal showed a reduction of 18%; Based on our TEA of coal-fired power plants, implementing the VDTSB for coal pretreatment could reduce the mercury capture capital and operating expenses by 36% and 38%, respectively, which exceeded the target goal of 25% reduction; A patent application was prepared, and the results were presented at the 2017 AIChE Annual Meeting (Minneapolis, MN).

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2023

Desolvation Processes in Channel Solvates of Niclosamide

The antiparasitic drug niclosamide (NCL) is notable for its ability to crystallize in multiple 1:1 channel solvate forms, none of which are isostructural. Here, using a combination of time-resolved synchrotron powder X-ray diffraction and thermogravimetry, the process-induced desolvation mechanisms of methanol and acetonitrile solvates are investigated. Structural changes in both solvates follow a complicated molecular-level trajectory characterized by a sudden shift in lattice parameters several degrees below the temperature where the desolvated phase first appears. Model fitting of kinetic data obtained under isothermal heating conditions suggests that the desolvation is rate-limited by the nucleation of the solvent-free product. The desolvation pathways identified in these systems stand in contrast to previous investigations of the NCL channel hydrate, where water loss by diffusion initially yields an anhydrous isomorph that converts to the thermodynamic polymorph at significantly higher temperatures. Taking the view that each solvate lattice is a unique “pre-organized” precursor, a comparison of the pathways from different starting topologies to the same final product provides the opportunity to reevaluate assumptions of how various factors (e.g., solvent binding strength, density) influence solid-state desolvation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu 1.81 S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.

36 MATERIALS SCIENCE↗
DOE OSTI2026

MoNbTi-based Refractory Multi-principal Element Alloy System: A Review of the Thermodynamic Phase Predictions, Formed Microstructures, and Mechanical Properties as a Function of the Fabrication Methods (AM versus SPS versus VAM)

Abstract Multi-principal element alloys, particularly of refractory compositions, are an increasingly popular candidate for extreme-environment applications, including for next-generation nuclear reactors and in other industries, such as biomedical and aerospace, due to their high strength. The ability to achieve solid-solution microstructures provides these alloys with improved mechanical properties; however, these microstructures are heavily composition- and processing-dependent. In this review, the multi-principal element alloy MoNbTi-based system (with Zr, V, and Cr additions) was selected to compare the effects of elemental composition and processing route on the resulting microstructures and mechanical properties. The review provides insight into identifying the optimal alloy composition and processing route for a balance of desired microstructure and mechanical properties.

Krogh, Kara↗
DOE OSTI2019

Computational Study of Short-Pulse Laser-Induced Generation of Crystal Defects in Ni-Based Single-Phase Binary Solid–Solution Alloys

Single-phase concentrated solid–solution alloys exhibit enhanced mechanical characteristics and radiation damage resistance, making them promising candidate materials for applications involving an exposure to rapid localized energy deposition. We use large-scale atomistic modeling to investigate the mechanisms of the generation of vacancies, dislocations, stacking faults, and twin boundaries in Ni, Ni 50 Fe 50 , Ni 80 Fe 20 , and Ni 80 Cr 20 targets irradiated by short laser pulses in the regime of melting and resolidification. The decrease in the thermal conductivity and strengthening of the electron–phonon coupling due to the intrinsic chemical disorder in the solid-solution alloys are found to have important implications on localization of the energy deposition and generation of thermoelastic stresses. The interaction of the laser-induced stress waves with the melting front is found to play a key role in roughening of the crystal–liquid interface and generation of dislocations upon the solidification. A common feature revealed in the structural analysis of all irradiated targets is the presence of high vacancy concentrations exceeding the equilibrium values at the melting temperature by about an order of magnitude. On the basis of the results of molecular dynamics simulations of solidification occurring at fixed levels of undercooling, the generation of vacancies is correlated with the velocity of the solidification front, and the processes responsible for creating the strong vacancy supersaturation are revealed. The suppression of the vacancy generation in the solid–solution alloys is also revealed and related to combined effect of enhanced vacancy mobility and higher energy of the vacancy formation in the alloy systems. The analysis of the first atomic shells surrounding the vacancy sites in Ni–Fe alloys uncovers the preference for the vacancy sites to be surrounded by Fe atoms and suggests that atomic-scale chemical heterogeneities may play an important role in defining the behavior and properties of the single-phase concentrated solid-solution alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Fabrication of 7075-0.25Sc-0.15Zr Alloy with Excellent Damping and Mechanical Properties by FSP and T6 Treatment

This study investigated the effects of Sc and Zr additions, friction stir processing (FSP), and subsequent solid solution and artificial aging (T6) treatment on the microstructure, damping capacity, and mechanical properties of 7075 Al alloy. The minor Sc and Zr additions promoted the grain refinement of this alloy during FSP and inhibited the growth of fine equiaxed grains in the FSP sample during subsequent T6 treatment. Thus, the fine equiaxed grain structure and high density of the η′ precipitated phase were simultaneously obtained in the 7075 Al alloy containing Sc and Zr after FSP and T6 treatment, and this sample exhibited superior mechanical properties and damping capacity to those of the 7075 Al alloy after T6 treatment. This work provides an effective strategy for preparing Al alloys with excellent damping capacity and mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

ExaCA: A performance portable exascale cellular automata application for alloy solidification modeling

Modeling the as-solidified grain structures that form during alloy processing is a critical component in understanding process-property relationships, particularly for additive manufacturing (AM) where grain structure is very sensitive to processing conditions. While cellular automata (CA)-based models have proven able to predict aspects of microstructure for several alloys and AM process conditions, long run times and large resource sets required limit the utility and the problem size to which existing CA models can be applied. As part of the ExaAM project, an initiative within the Exascale Computing Project (ECP) to develop, test, and optimize an exascale-capable coupled and self-consistent model of AM parts, we developed ExaCA (https://github.com/LLNL/ExaCA) for the liquid–solid phase transformation in the wake of AM melt pools. The CA-based code is parallelized using MPI and the Kokkos programming model, the latter enabling simulation on both CPUs and GPUs within a single-source implementation. Here, we detail the steps taken to transform a baseline, MPI-based CA code into one that is performant on CPUs and GPUs. Performance testing of ExaCA on Summit (a pre-exascale machine at Oak Ridge National Laboratory) was used to quantify CPU–GPU speedup comparing with equal numbers of nodes. Testing showed comparable CPU performance to the MPI-only CA code and a 5-20x speedup when running AM-based test problems using GPUs. The improved performance of CA through GPU utilization and the performance portable nature of ExaCA will enable accurate part-scale modeling by harnessing the power of current and future generations of high performance computing resources. Future work will include improving the strong scaling of ExaCA on GPUs by reducing load imbalance associated with the locality of the problem, and continuing performance optimization across exascale hardware.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enhancement of Two Heterogeneous Reactions in the Production of the Medical Isotope 188 W

We report the efficiency of heterogeneous reactions is influenced by kinetic conditions with an emphasis on reactants in different phases to have effective interactions. Optimal interactions of reactants rely on the rational design of the equipment and engineering parameters for the reaction process, especially for the process on a large scale. 188 W production at the Oak Ridge National Laboratory is such an example. In processing the irradiated 186 W metal target for the 188 W product, two of the heterogeneous reactions are essential ones: (1) the gas–solid reaction of O 2 + W to form WO 3 and (2) the gas–liquid reaction of OsO 4 being absorbed by the NaOH sorbent. Better understanding of the two reactions has led to revisions to the design of the quartz reaction vessel (gas–solid reaction) and the scrubbing system (gas–liquid reaction). The optimized quartz vessel resulted in less heating hours, whereas a more efficient OsO 4 scrubbing system ensured that all volatile OsO 4 was qualitatively captured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Long-Term 13 C Uptake by 12 C-Enriched Calcite

Knowledge of the exchange of carbon isotopes between dissolved inorganic carbon and calcite minerals is of long-standing importance for the interpretation of sedimentary paleoclimate records and 14 C transport in the geosphere. To assess the mechanism and rates of carbon isotope exchange, we equilibrated 12 C-pure synthetic calcite particles in water, first in a glovebox and then in contact with atmospheric P CO 2 and 13 C/ 12 C ratio, at two different temperatures. Cavity ring-down infrared spectroscopy δ 13 C measurements of the solid revealed sustained 13C incorporation for over a period of 500 days (21 °C) and 125 days (50 °C). We developed a quantitative model for recrystallization and isotope exchange, assuming that the interfacial free energy provides a thermodynamic driving force for the growth of larger particles at the expense of smaller ones. Furthermore, this Ostwald ripening model did not reproduce the kinetics of 13C uptake and required greater coarsening than observed. Rather, the data were best explained by a mechanism involving surface exchange and solid-phase diffusion of 13C into the particles with an inferred effective diffusion constant at 21 °C of about 10 –25 m 2 /s. Although this work cannot rule out the possibility that structural or chemical aspects of the synthetic particles enabled faster 13 C uptake than could be observed in natural systems, this study adds to the body of the recent work, suggesting that fast exchange processes are possible, likely through grain boundaries and other defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Impact of Liquid-Vapor to Liquid-Liquid-Vapor Phase Transitions on Asphaltene-Rich Nanoaggregate Behavior in Athabasca Vacuum Residue + Pentane Mixtures

The bulk phase behavior of heavy oil + alkane mixtures and the behavior of the asphaltenes that they contain are topics of importance for the design and optimization of processes for petroleum production, transport, and refining and for performing routine saturates, aromatics, resins, and asphaltenes (SARA) analyses. In prior studies, partial phase diagrams and phase behavior models for Athabasca vacuum residue (AVR) comprising 32 wt % pentane asphaltenes + n-alkanes were reported. For mixtures with pentane, observed phase behaviors included single-phase liquid as well as liquid–liquid, liquid–liquid–vapor, and liquid–liquid–liquid–vapor regions. Dispersed solids were detected under some conditions as well but not quantified. In this work, small-angle X-ray scattering (SAXS) is used to study nanostructured materials in liquid phases present in AVR + n-pentane mixtures from 50 to 170 °C at mixture bubble pressure. The investigation focuses on the impact of the transition from a single AVR-rich liquid to co-existing pentane-rich and AVR-rich liquids on the nanostructure and the nanostructures most resistant to aggregation as the pentane composition axis is approached. Background scattering subtraction was performed using global mixture composition. The robustness of this assumption with respect to values obtained for coefficients appearing in a two level Beaucage unified equation fit is demonstrated. The nanostructured material is shown to arise at two length scales from 1 to 100 wt % AVR. Smaller nanostructures possess mean radii less than 50 Å, while the larger nanostructures possess mean radii greater than 250 Å. The addition of pentane to the AVR causes an increasingly large fraction of the large and small nanostructures to grow in size. Only nanostructures resistant to aggregation remain in the pentane-rich phase as the 0 wt % AVR axis is approached. Step changes in aggregation identified from changes in average radius of gyration, scattering coefficients, and surface/volume ratios arise at the liquid–vapor to liquid–liquid–vapor transition (~40 wt % pentane) and within the liquid–liquid–vapor region (~90 wt % pentane). The temperature is shown to have a limited effect on the mean size and structure of the nanostructured material present, irrespective of global composition.

Long, Bingwen↗
DOE OSTI2022

Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics

Understanding and mitigating filament formation, short-circuit and solid electrolyte fracture is necessary for advanced all-solid-state batteries. Here, we employ a coupled far-field high-energy diffraction microscopy and tomography approach for assessing the chemo-mechanical behaviour for dense, polycrystalline garnet (Li 7 La 3 Zr 2 O 12 ) solid electrolytes with grain-level resolution. In situ monitoring of grain-level stress responses reveals that the failure mechanism is stochastic and affected by local microstructural heterogeneity. In this work, coupling high-energy X-ray diffraction and far-field high-energy diffraction microscopy measurements reveals the presence of phase heterogeneity that can alter local chemo-mechanics within the bulk solid electrolyte. These local regions are proposed to be regions with the presence of a cubic polymorph of LLZO, potentially arising from local dopant concentration variation. The coupled tomography and FF-HEDM experiments are combined with transport and mechanics modelling to illustrate the degradation of polycrystalline garnet solid electrolytes. The results showcase the pathways for processing high-performing solid-state batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Numerical Simulation of an Industrial Fluid Catalytic Cracking Regenerator

Fluid catalytic cracking (FCC) is one of the most important conversion processes in petroleum refineries, and the FCC regenerator is a key part of an FCC unit utilized in the recovery of solid catalyst reactivity by burning off the deposited coke on the catalyst surface. Furthermore, a three-dimensional multiphase, multispecies reacting flow computational fluid dynamics (CFD) model was established to simulate the flow and reactions inside an FCC regenerator. The Euler–Euler approach, where the two phases (gas and solid) are considered to be continuous and fully interpenetrating, is employed. The model includes gas–solid momentum exchange, gas–solid heat exchange, gas–solid mass exchange, and chemical reactions. Chemical reactions incorporated into the model simulate the combustion of coke which is present on the catalyst surface. We validated the simulation results using plant data.

42 ENGINEERING↗
DOE OSTI2024

Surface Structure of Reacting Solid Ramjet Fuels

Solid fuel ramjets are a developing technology that will enable extended range for supersonic vehicles. The simplicity of the system in terms of moving parts results in the performance being dictated by the solid fuel combustion processes. The physics near the surface, particularly in the fuel-rich recirculation zone, are challenging to resolve due to flow opacity. Here, regression rate measurements of hydroxyl-terminated polybutadiene from a miniature, portable slab burner are reported. Mass-averaged regression rates agree with correlations from the literature, suggesting that the proper physics in the burner are captured. Synchrotron-based phase-contrast imaging is used to quantify local surface features, including a multiphase froth layer, molten polymer transport, and local regression rate measurements in the recirculation zone. Regression rates near the inlet are less than the mass-averaged values, whereas near the reattachment point the local value exceeds the mass-averaged values. Further, the observed froth layer is as large as 2 mm near the inlet and decreases to sub-millimeter thicknesses near the reattachment point. An analytical heat transfer model is used to quantify the influence of the surface froth layer on the regression rates. Results indicate that the froth layer has an insulating effect and will reduce the local regression rate.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2021

Ternary borides and borohydrides for hydrogen storage and method of synthesis

A method and a system is provided for obtaining solid-state hydrogen storage and release in materials with at least theoretical loaded hydrogen densities of 11 wt % or greater that can deliver hydrogen and be recharged at moderate temperatures enabling incorporation into hydrogen storage systems suitable for transportation applications. These materials comprise ternary boride materials comprising certain light transition metals and alkaline or alkaline earth metals, and ideally have no or very little phase separation. A process of making these materials is also provided.

Stavila, Vitalie↗
DOE OSTI2015

Effect of sintering time on structural, microstructural and chemical composition of Ni-doped lanthanum gallate perovskites

This work reports the effect of two different sintering times, 6 and 48 h on the structural, microstructural, and chemical features of Ni-doped La{sub 0.90}Sr{sub 0.10}GaO{sub 3.00−δ}. Independently of the sintering time, La{sub 0.90}Sr{sub 0.10}Ga{sub 1−x}Ni{sub x}O{sub 3.00−δ} (where x=0.10, and 0.20 (mol)) presents a rhombohedral symmetry with a lattice volume that decreases when NiO dopant increases. Besides the perovskite, LaSrGa{sub 3.00}O{sub 7.00} (nominal composition) is present as second phase in all cases. When the samples are doped with NiO, the peaks of this second phase are shifted with respect to the peaks of the pure phase. These shifts suggest that this second phase could admit some Ni ions in its structure. According to the XRD patterns, the amount of the latter phase is larger when sintering time is increased. Electron probe microanalysis (EPMA) indicated that the matrix of the samples sintered for 6 h is constituted by a perovskite with an experimental composition very close to the nominal one. However, when the samples are sintered for 48 h the matrix of each sample is constituted by two perovskites; both with compositional deviations with respect to their nominal one. In particular, a significant Sr depletion compensated by a La increment in the A site is observed. Those compositional deviations could be mainly due to the diffusion of the cations in the bulk and/or from the bulk to the surface of the samples. That diffusion can favour the formation, not only, of a second perovskite with a different composition in relation with the first one formed, but also, the formation of second phases. In addition, a very slight broadening of Bragg peaks of the perovskites sintered for 48 h is observed by XRD and can be related to the presence of two different perovskites in each sample according to EPMA results. By BSEM and EPMA analyses La{sub 4.00}Ga{sub 2.00}O{sub 9.00} (nominal composition) is also observed as second phase when samples are treated for 48 h. - Graphical abstract: Typical microstructures, observed by FEG-SEM, of La{sub 0.90}Sr{sub 0.10}Ga{sub 1−x}Ni{sub x}O{sub 3.00−δ} materials with x=0.00 and 0.10 (nominal compositions) and sintered at 1450 °C for 48 h after polishing and thermal etching are shown. Lighter grey grains with a bimodal grain size are observed and according to XEDS analysis correspond to two perovskites with different experimental compositions (labelled as 1 and 2 for x=0.00 and labelled as 4 and 5 for x=0.10, respectively), meanwhile the darker grey phases correspond to LaSrGa{sub 3.00}O{sub 7.00} (labelled as 3 for x=0.00) and LaSr(Ga{sub 1−y′},Ni{sub y′}){sub 3.00}O{sub 7.00} (labelled as 6 for x=0.10), respectively. - Highlights: • When NiO is introduced into La{sub 0.90}Sr{sub 0.10}GaO{sub 3.00−δ} a change in symmetry is produced. • A significant Sr depletion in the A-site of perovskites treated for 48 h is observed. • Compositional deviations could be due to a thermally-activated diffusional process. • The phase purity of these materials is deteriorated when the sintering time is extended.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

New mechanistic insight into the oxygen reduction reaction on Ruddlesden–Popper cathodes for intermediate-temperature solid oxide fuel cells

Ruddlesden–Popper (R–P) phase materials have been investigated widely as cathode candidates for IT-SOFCs. However, widespread application of R–P phase cathodes demands further improvement in electrode activity whose progress is hindered by the limited information in the oxygen reduction reaction (ORR). The ORR mechanism for the R–P phase is therefore investigated in this paper using (LaSr) 2 NiO 4±δ as an example. Accurate characterization of the surface oxygen exchange process is realized by developing thin and dense polycrystalline LSNO layers via a versatile spray-modified pressing method we invented before to avoid perceptible bulk diffusion contribution, surface enrichment and geometry complication. Hence, the governing factors of the ORR are identified as oxygen adsorption and incorporation based on the findings in reaction orders from electrochemical impedance spectroscopy (EIS), stoichiometry-related chemical capacitance and intrinsic anisotropic properties.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2017

Influence of humidity, temperature, and annealing on microstructure and tensile properties of electrospun polyacrylonitrile nanofibers

This study investigates the microstructure and mechanical properties of electrospun nanofibers from polyacrylonitrile (PAN)-dimethylformamide (DMF) solution at different relative humidity (RH) in the range from 14% to 60% and two different temperatures (20 °C and 40 °C). Nanofibers produced at low RH (22% or less at 20 °C) exhibit relatively smooth surface and solid core, whereas at higher RH (30% or higher at 20 °C) rough surface and porous core are observed. The resulting morphology is explained by means of H 2 O/DMF/PAN ternary phase diagram. At higher RH, the water diffusion into polymer-solution jet brings thermodynamic instability into the system leading to separation of polymer-rich phase and polymer-lean phase, where the later contributes to porosity. Higher process temperature (40 °C) yields larger miscibility area in the ternary phase diagram leading to formation of porous structure at relatively higher RH (40%). Tensile strength of nanofibrous yarns is found to vary from 80 MPa to 130 MPa depending on the processing temperature and RH. The amount of porosity is found to affect the tensile properties of nanofibers most significantly, although diameter and crystallinity play important role. Annealing is found to alleviate surface roughness and porosity and increase crystallinity. Furthermore, tensile strength of nanofibrous yarns is found to improve by up to 25% after annealing.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermal Processing Conditions for the Synthesis of Near Theoretical Density Li 5 La 3 Ta 2 O 12 Ceramics for Ceramic Dual-Mode Detectors

A family of Li-containing garnet compounds, extensively investigated for Li-ion solid electrolyte applications, show great potential to be developed into transparent ceramic dual-mode scintillators. In particular, Li 5 La 3 Ta 2 O 12 (LLTaO) shows promise as an efficient dual-mode scintillator due to its high Li content, high density, non-hygroscopicity, and high effective-Z. Often the synthesis of LLTaO ceramics involves solid state processing techniques starting with oxide and carbonate powders, calcining, sintering for the removal of residual porosity, and post-processing. This study focuses on two objectives: (1) establishing thermal processing boundary conditions for a flexible alkoxide-based sol-gel method for synthesizing fine-grained powders; and (2), consolidating powders via hot-pressing to form high-density ceramics. In this study, near single-phase ceramics were achieved by hot-pressing sol-gel powders with varying amounts of excess Li. Rietveld refinements were used to analyze X-ray diffraction data and provide a quantitative evaluation of the phases present in the hot pressed ceramics. Some of the diffraction data showed large low angle peak asymmetry, suggesting the presence of two cubic Li 5 La 3 Ta 2 O 12 garnet phases with different lattice parameters. Depending on the synthesis and processing conditions, the refinement revealed ~ 90 wt% concentration of a phase with a ≈ 12.8 Å and ~ 10 wt% concentration of a phase with a ≈ 12.9 Å, indicating a remaining excess of Li in the hot pressed ceramics in the large lattice parameter phase. These synthesis experiments allowed for the determination of a baseline for Li loss during hot-pressing. X-ray excited radioluminescence and photoluminescence excitation and emission spectra were obtained from the hot pressed ceramics. In conclusion, the measured emission spectra featured broad tantalate emission and line emissions likely from a rare-earth impurity.

36 MATERIALS SCIENCE↗