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At least 829 records · Page 46

Uncovering the Size-dependent Thermal Solid Transformation of Akaganéite

Investigating the structural evolution and phase transformation of iron oxides is crucial for gaining a deeper understanding of geological changes on diverse planets and preparing oxide materials suitable for industrial applications. In this study, we employed in-situ heating techniques in conjunction with transmission electron microscopy (TEM) observations and ex-situ characterization to thoroughly analyze the thermal solid-phase transformation of akaganéite one-dimensional (1D) nanostructures with varying diameters. Our findings offer compelling evidence for a size-dependent morphology evolution in akaganéite 1D nanostructures, which can be attributed to the transformation from akaganéite to maghemite (?-Fe2O3) and subsequent crystal growth. Specifically, we observed that akaganéite nanorods with a diameter of around 50 nm transformed into hollow polycrystalline maghemite nanorods, which demonstrated remarkable stability without arresting crystal growth under continuous heating. In contrast, smaller akaganéite nanoneedles or nanowires with a diameter ranging from 20 to 8 nm displayed a propensity for forming single-crystal nanoneedles or nanowires through phase transformation and densification. By manipulating the size of the precursors, we have developed a straightforward method for the synthesis of single-crystal and polycrystalline maghemite nanowires through solid-phase transformation. These significant findings provide new insights into the size-dependent structural evolution and phase transformation of iron oxides at the nanoscale.

Wang, Xiang↗

Correlation of Thermally Induced Pores with Microstructural Features Using High Energy X-rays

Combined application of a near-field High Energy Diffraction Microscopy measurement of crystal lattice orientation fields and a tomographic measurement of pore distributions in a sintered nickel-based superalloy sample allows pore locations to be correlated with microstructural features. Furthermore, measurements were carried out at the Advanced Photon Source beamline 1-ID using an X-ray energy of 65 keV for each of the measurement modes. The nickel superalloy sample was prepared in such a way as to generate significant thermally induced porosity. A three-dimensionally resolved orientation map is directly overlaid with the tomographically determined pore map through a careful registration procedure. The data are shown to reliably reproduce the expected correlations between specific microstructural features (triple lines and quadruple nodes) and pore positions. With the statistics afforded by the 3D data set, we conclude that within statistical limits, pore formation does not depend on the relative orientations of the grains. The experimental procedures and analysis tools illustrated are being applied to a variety of materials problems in which local heterogeneities can affect materials properties.

36 MATERIALS SCIENCE↗

DRACS thermal performance evaluation for FHR

Direct Reactor Auxiliary Cooling System (DRACS) is a passive decay heat removal system proposed for the Fluoride-salt-cooled High-temperature Reactor (FHR) that combines coated particle fuel and a graphite moderator with a liquid fluoride salt as the coolant. The DRACS features three coupled natural circulation/convection loops, relying completely on buoyancy as the driving force. These loops are coupled through two heat exchangers, namely, the DRACS Heat Exchanger and the Natural Draft Heat Exchanger. In addition, a fluidic diode is employed to minimize the parasitic flow into the DRACS primary loop and correspondingly the heat loss to the DRACS during normal operation of the reactor, and to keep the DRACS ready for activation, if needed, during accidents. To help with the design and thermal performance evaluation of the DRACS, a computer code using MATLAB has been developed. This code is based on a one-dimensional formulation and its principle is to solve the energy balance and integral momentum equations. By discretizing the DRACS system in the axial direction, a bulk mean temperature is assumed for each mesh cell. The temperatures of all the cells, as well as the mass flow rates in the DRACS loops, are predicted by solving the governing equations that are obtained by integrating the energy conservation equation over each cell and integrating the momentum conservation equation over each of the DRACS loops. In addition, an intermediate heat transfer loop equipped with a pump has also been modeled in the code. This enables the study of flow reversal phenomenon in the DRACS primary loop, associated with the pump trip process. Experimental data from a High-Temperature DRACS Test Facility (HTDF) are not available yet to benchmark the code. A preliminary code validation is performed by using natural circulation experimental data available in the literature, which are as closely relevant as possible. The code is subsequently applied to the HTDF that is under construction at the Ohio State University.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Analytical Determination of Radioactive Strontium and Cesium by Thermal Ionization Mass Spectrometry

Thermal ionization mass spectrometry (TIMS) has been evaluated for the detection of the radioactive isotopes of strontium and cesium. The instrument was investigated for the analysis of isotopic ratios of 89Sr to 90Sr and 135Cs to 137Cs in the presence of atomic isobars (Y and Zr for Sr analysis and Ba for Cs analysis). Signicant discrimination using TIMS was found for both Sr and Cs through evaluation using stable isotopes. Fusion procedures with different flux were evaluated for preparation of sample matrices. Chemical separations were developed and used after fusion to isolate the Sr and Cs from a prepared background matrix (i.e., Montana Soil). A graded approach, increasing in stable background isotopes, was performed to monitor the chemistry and instrument response. A thermal neutron irradiation was performed to produce a sample that contained the radioisotopes of Sr and Cs. Even though the irradiated sample was not a certified standard it does provide accurate expectation values via published, well understood cumulative fission yield data. The results presented in this work correlate extremely well with the published data. Furthermore, a significant decrease in uncertainty (by a factor of 5 { 10) was found for the isotopic ratios measured with TIMS compared to the published values.

TIMS, environmental contamination, radiostrontium,↗

Thermal expansion in UO 2 determined by high-energy X-ray diffraction

Here we present crystallographic analyses of high-energy X-ray diffraction data on polycrystalline UO2 up to the melting temperature. The Rietveld refinements of our X-ray data are in agreement with previous measurements, but are systematically located around the upper bound of their uncertainty, indicating a slightly steeper trend of thermal expansion compared to established values. This observation is consistent with recent first principles calculations.

Guthrie, M.↗

On α' precipitate composition in thermally annealed and neutron-irradiated Fe- 9-18Cr alloys [On α' composition in thermally annealed and neutron-irradiated Fe- 9-18Cr alloys]

Ferritic-martensitic steels are a leading candidate for many nuclear energy applications. However, precipitation of nanoscale a’ precipitates during thermal aging at temperatures above 450 °C, or during neutron irradiation at lower temperatures, makes these Fe-Cr steels susceptible to embrittlement. To complement the existing literature, a series of Fe-9 to 18 Cr alloys were neutron-irradiated at temperatures between 320 and 455 °C up to fluences of 20 dpa. In addition, post-irradiation annealing treatments at 500 and 600 °C were performed on the neutron-irradiated Fe-18 Cr alloy to validate the a-a’ phase boundaries. The microstructures were characterized using atom probe tomography and the results were analyzed in light of the existing literature. In conclusion, under neutron irradiation and thermal annealing, the measured a’ concentrations ranged from ~81 to 96 at.% Cr, which were discussed in terms of temperature, precipitate size, technique artefacts, and, possibly, cascade ballistic mixing.

36 MATERIALS SCIENCE↗

The effect of oxygen enrichment on soot formation and thermal radiation in turbulent, non-premixed methane flames

Non-premixed oxy-fuel combustion of natural gas is used in industrial applications where high-intensity heat is required, such as glass manufacturing and metal forging and shaping. In these applications, the high flame temperatures achieved by oxy-fuel combustion increase radiative heat transfer to the surfaces of interest and soot formation within the flame is desired for further augmentation of radiation. However, the high cost of cryogenic air separation has limited the penetration of oxy-fuel combustion technologies. New approaches to air separation are being developed that may reduce oxygen production costs, but only for intermediate levels of oxygen enrichment of air. To determine the influence of oxygen enrichment on soot formation and radiation, we developed a non-premixed coannular burner in which oxygen concentrations and oxidizer flow rates can be independently varied, to distinguish the effects of turbulent mixing intensity from oxygen enrichment on soot formation and flame radiation. Local radiation intensities, soot concentrations, and soot temperatures have been measured using a thin-film thermopile, planar laser-induced incandescence (LII), and two-color imaging pyrometry, respectively. The measurements show that soot formation increases as the oxygen concentration decreases from 100% to 50%, helping to moderate a decrease in overall flame radiation. An increase in turbulence intensity has a marked effect on flame height, soot formation and thermal radiation, leading to decreases in all of these. The soot temperature decreases with a decrease in the oxygen concentration and increases with an increase in turbulent mixing intensity. Altogether, the results suggest that properly designed oxygen-enriched burners that enhance soot formation for intermediate levels of oxygen purity may be able to achieve thermal radiation intensities as high as 85% of traditional oxy-fuel burners utilizing high-purity oxygen.

03 NATURAL GAS↗

In-Situ Thermal Imaging for Single Layer Build Time Alteration in Large-Scale Polymer Additive Manufacturing

Ideally, objects are constructed as quickly as possible; however, short build times for a layer can present an issue. Short layer build times do not provide enough time for the material to cool sufficiently. As a result, an object cannot support its own weight nor deal with overhanging features. Additionally, the generation of support structures may be impractical either due to geometry or, in the case of large-scale polymer additive manufacturing, due to being difficult to remove. To address these issues, researchers at Oak Ridge National Laboratory’s Manufacturing Demonstration Facility investigated the use of a thermal camera mounted to a gantry to collect data on an object under construction. This data provided feedback for an in-situ control system to adjust layer build times. Adjustments were made in the form of additional waiting to allow the material to cool to specific thermal thresholds. This additional cooling time allowed the construction of objects with low layer build times or overhanging features that would have otherwise failed.

Borish, Michael↗

Direct Prelithiation of Silicon-Based Composite Electrodes via Island-like Thermal Evaporation

Irreversible losses of Li during solid electrolyte interface (SEI) conditioning is a key contributor to the lower specific capacities observed in silicon-containing Li-ion batteries. Herein, thermal evaporation of between 1 and 20 µm of Li onto Si-based composite anodes has been investigated as a prelithiation method to account for such losses. To account for mechanical strain caused by Li-Si alloying during the deposition, a stainless-steel mesh is applied to the electrodes before prelithiation to form “island-like” deposition on the electrode surface. The open circuit potential was also found to decrease as a function of increased Li evaporation, consistent with the potentials of electrochemically prepared LixSi alloys. Prelithiating to account for irreversible Li losses to SEI formation resulted in full cells with a 15.8% increase in initial coulombic efficiency and a 47.8% reduction in irreversible capacity loss after SEI formation cycling. Subsequent C/3 cycling showed up to a 62.9% increase in specific capacity in prelithiated cells. X-ray photoelectron spectroscopy (XPS) revealed differences in the SEI composition that was formed by electrochemical cycling and reactively formed in prelithiated cells upon exposure to Gen2 + 3% FEC electrolyte. The reactively formed SEI from the spontaneous reaction with lithiated silicon was carbonate-rich while the electrochemical SEI formation showed significantly more LiPFx species, which could play a role in overall cycling performance.

Musgrove, Amanda↗

In situ characterization of metastable Pb3O5 and Pb2O3 phases during thermal decomposition of PbO2 to PbO

Nonstoichiometric lead oxides play a key role in the formation and cycling of the positive electrodes in a lead acid battery. These phases have been linked to the underutilization of the positive active material but also play a key role in the battery’s cycle life, providing inter-particle adhesion and the connection to the underlying lead grid. Similar phases have previously been identified by mass loss or color change during thermal annealing of PbO2 to PbO, suggesting that at least two intermediate PbOx phases exist. Using multiple in situ analysis techniques (powder diffraction, x-ray absorption, x-ray photoelectron spectroscopy) and ex situ nuclear magnetic resonance measurements, the structural conversion and changes in the lead oxidation states were identified during this process. Isolation of the PbOx phases enabled confirmation of Pb3O5 and Pb2O3 by diffraction and the first 207Pb NMR measurement of these intermediates.

Kinnibrugh, Tiffany L.↗

Prospect of Thermal Shock Induced Healing of Lithium Dendrite

Dendritic growth plagues the development of rechargeable lithium metal anodes. Recently, it has been reported that self-heating of the cell provides a mitigation strategy for suppressing dendrites. In order to study this phenomenon, we extend our recently developed nonlinear phase-field model to incorporate an energy balance equation allowing a full thermally coupled electrodeposition model using the open-source software package MOOSE. In this study, we consider the interplay between ionic transport and electrochemical reaction rate as a function of temperature and explore the possibility of using thermal shock induced dendrite suppression. We discover that, depending on the electrochemical reaction barrier and ionic diffusion barrier, self-heating could accelerate (larger reaction barrier) or decelerate (larger diffusion barrier) dendrite formation. Given that the electrolyte constituents can be used to tune both barriers, this study could provide an important avenue to exploit the self-heating effect favorably through electrolyte engineering.

25 ENERGY STORAGE↗

Tuning the Moisture and Thermal Stability of Metal–Organic Frameworks through Incorporation of Pendant Hydrophobic Groups

An isostructural series of NbO-type porous metal–organic frameworks (MOFs) with different dialkoxy-substituents of formula Cu 2 (TPTC-OR) (TPTC-OR = 2',5'-di{alkyl}oxy-[1,1':4',1"-terphenyl]-3,3",5,5"-tetracarboxylate, R = Me, Et, n Pr, n Hex) has been synthesized and characterized. The moisture stability of the materials has been evaluated, and a new superhydrophobic porous MOF has been identified. The relationship between pendant side chain length and thermal stability has been analyzed by in situ synchrotron powder X-ray diffraction, showing decreased thermal stability as the side chain length is increased, contradictory to thermogravimetric decomposition studies. Additionally, the four materials exhibit moderate Brunauer–Emmett–Teller (BET) and Langmuir surface areas (1127–1396 m 2 g –1 and 1414–1658 m 2 g –1 ) and H 2 capacity up to 1.9 wt % at 77 K and 1 bar.

Makal, Trevor A.↗