Targeted uranium recovery from complex alloys using fluoride volatility
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Shear deformation has been highlighted in multiple research efforts for its ability to impart mechanical properties improvements and unique microstructures. When used to process and densify powdered material, these shear-based consolidation techniques are commonly referred to as friction consolidation (FC). In this paper, we have examined the microstructural evolution from compacted Cu and Ni powders to a consolidated Cu0.5Ni0.5 alloy. We have shown various stages of porosity reduction and preferential deformation being accommodated by the more ductile material early in the process, leading to formation of a tortuous microstructural zone. Porosity reduction was extensive, decreasing from ~65% in the unprocessed powder to ~1% in the fully consolidated alloy. The final consolidated alloy showed roughly a 2X hardness improvement over the unalloyed, compacted material. Unique aspects of this work include demonstration of the ability to use FC processing to produce a submicron and equiaxed grain size in samples within a 0.5 to 2 minute processing time.
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The electronic properties relevant to superconductivity are reported for bulk Ta-Hf and Ta-Zr body centered cubic alloys, in a large part to determine whether their properties are suitable for potential use in superconducting qbits. The body centered cubic unit cell sizes increase with increasing alloying. Here, the results of magnetic susceptibility, electrical resistivity, and heat capacity characterization are reported. While elemental Ta is a type I superconductor, the alloys are type II strong coupling superconductors. Although decreasing the electron count per atom is expected to increase the density of electronic states at the Fermi level and thus the superconducting transition temperature (T c ) in these systems, we find that this is not sufficient to explain the significant increases in the superconducting T c 's observed.
The susceptibility to adiabatic shear banding (ASB) of tungsten heavy alloys (WHAs) is a key factor to determine their penetration performance for kinetic energy penetrators (KEPs). This work reports a novel WHA with strong susceptibility to ASB that uses a precipitation-hardening high-entropy alloy (HEA) as the binding phase of W particles. The results find that nanoscale L12 precipitates and high dislocation density in the matrix contribute a high dynamic yield strength of ~2300 MPa. Also, a narrow ASB with a width of ~12 μm forms in the novel WHA, which is only 6% of the width of ASB in traditional WHAs like W-NiFe, exhibiting a great susceptibility to ASB. The redissolution of precipitates into the matrix because of temperature rise during shearing could sharply soften the shearing location, which is suggested to be a very important factor of destabilizing mechanism to promote the development of ASB.
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Element redistributions after initial gaseous oxidation of a Ni38Cr22Fe20Mn10Co10 (at%) multi-principle element alloy at 120°C and 300°C is captured via psuedo in situ atom probe tomography. All cations contribute to the oxide in both conditions, consisting of a Cr-rich inner oxide and Fe, Mn, Co and Ni-rich outer oxide. At the lower temperature, Ni tends to be trapped at the outer/inner oxide interface, while Ni enriches at the oxide/metal interface at higher temperature in tandem with Cr metal depletion. These observations confirm oxidation of complex alloys involves the formation of metastable, multi-layered oxide films, with a distinct tendency for solute trapping.
A computational thermodynamics approach has been employed to design CoCrFeMnNi-based medium- and high-entropy alloys (M/HEAs) with systematically varied compositions (Co(( 80-X )/ 2 )Cr(( 80-X )/ 2 )Fe X Mn 10 Ni 10 with x = 30, 40, and 50 at.%) and phase stability. Since the formation of sigma phase, usually brittle and undesirable, is a common concern, when this class of alloys is subjected to elevated temperatures (600–1000 °C), predicting its formation becomes essential. Thus, its formation and the phase equilibria were studied using the CALPHAD method, and two empirical methods, namely, valence electron concentration (VEC) and paired sigma-forming element (PSFE). Isothermal aging treatments at 900–1100 °C for 20 h were performed, since CALPHAD and VEC/PSFE predictions diverged. Both prediction methods were compared with experimental characterization by a combination of scanning electron microscopy and high-energy synchrotron X-ray diffraction. In conclusion, the predictions from the VEC/PSFE and CALPHAD calculations (depending on the database used) were shown to be quite accurate.
The selective production of C3+ olefins from renewable feedstocks, especially via C1 and C2 platform chemicals, is a critical challenge for obtaining economically viable low-carbon middle distillate transportation fuels (i.e., jet and diesel). Here, we report a multifunctional catalyst system composed of Zn-Y/Beta and “single-atom” alloy (SAA) Pt-Cu/Al2O3 which selectively catalyzes ethanol-to-olefins (C3+, ETO) valorization in the absence of cofed hydrogen, forming butenes as the primary olefin products. Beta zeolites containing predominately isolated Zn and Y metal sites catalyze ethanol upgrading steps (588 K, 3.1 kPa ethanol, ambient pressure) regardless of cofed hydrogen partial pressure (0-98.3 kPa H2), forming butadiene as the primary product (60% selectivity at 87% conversion). The Zn-Y/Beta catalyst possesses site-isolated Zn and Y Lewis acid sites (at ~7 wt% Y) and Brønsted acidic Y sites, the latter of which has been previously uncharacterized. A secondary bed of SAA Pt-Cu/Al2O3 selectively hydrogenates butadiene to butene isomers at a consistent reaction temperature using hydrogen generated in situ from ethanol-to-butadiene (ETB) conversion. This unique hydrogenation reactivity at near-stoichiometric hydrogen and butadiene partial pressures is not observed over monometallic Pt or Cu catalysts, highlighting these operating conditions as a critical SAA catalyst application area for conjugated diene selective hydrogenation at high reaction temperatures (>573 K) and low H2/diene ratios (e.g., 1:1). Single-bed steady state selective hydrogenation rates, associated apparent hydrogen and butadiene reaction orders, and DFT calculations of the Horiuti-Polanyi reaction mechanisms indicate that the unique butadiene selective hydrogenation reactivity over SAA Pt-Cu/Al2O3 reflects lower hydrogen scission barriers relative to monometallic Cu surfaces and limited butene binding energies relative to monometallic Pt surfaces. DFT calculations further indicate the preferential desorption of butene isomers over SAA Pt-Cu(111) and Cu(111) surfaces while Pt(111) surface favors subsequent butene hydrogenation reactions to form butane over butene desorption events. Under operating conditions without of hydrogen cofeeding, this combination of Zn-Y/Beta and SAA Pt-Cu catalysts can selectively form butenes (65% butenes, 78% C3+ selectivity at 94% conversion) and avoid butane formation using only in situ generated hydrogen, avoiding costly hydrogen cofeeding requirements that hinder many renewable energy processes.
The volumetric changes of silicon electrodes, along with the strong adhesive properties of certain binders, can lead to plastic deformation of the current collector and create damage in the electrode coating. Here, in this study, we report a detailed study of silicon coatings on a high-tensile alloy (HTA) foil of copper with strength over twice that of conventional copper foils. The HTA current collectors with high mechanical strength can mitigate plastic deformation upon continuous cycling. At moderate areal capacities (2.5–3 mAh cm −2 ), conventional copper foils show significant wrinkling after only a few electrochemical cycles, whereas the HTA foils remain intact. We demonstrate viability of the HTA foils in large format xx6395 pouch cells, in which the HTA current collectors remain intact even at an areal capacity of 4.5 mAh cm −2 ; in contrast, wrinkles form in conventional copper current collectors increasing the likelihood of lithium plating. Computational studies show that stresses generated during cycling of silicon electrodes are very high in the current collector and at the current collector-coating interface, explaining the wrinkling of conventional Cu foils. Our studies highlight importance of current collector to solve the electrochemical and chemo-mechanical performance challenges associated with high-loading silicon electrodes.
This work builds on our previous investigation of the room temperature fatigue cracking mechanisms of an A356 Al alloy. Here, we analyze the elevated temperature fatigue cracking mechanisms in cast and friction stir processed (FSP) A356, and contrast them with the room temperature behavior. Two sets of FSP parameters were used to modify the microstructure of the cast alloy. After heat treatment, both the FSPed microstructures exhibited severe abnormal grain growth (AGG) leading to a very wide grain size distribution (from a few microns to a few millimeters). During room temperature fatigue tests, the FSP conditions exhibited significant improvements in fatigue lives, even up to an order of magnitude. However, with increasing temperature, the difference in the performance of the FSPed and Cast microstructures decreased until, at 200 °C, all three microstructural conditions exhibited similar fatigue response. Detailed electron back scattered diffraction (EBSD) imaging of failed fatigue specimens was used to study crack behavior. At room temperature, cracks initiated at defect sites or along persistent slip bands (PSBs) and propagated transgranularly. The grain boundaries acted as barriers to crack growth. At elevated temperatures, there was a complete role reversal of the grain boundaries. Cracks initiated along grain boundaries and propagated intergranularly in all microstructures. Below, we explore this transition of the cracking mechanism in detail.
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Parabolic rate constants, k p , were collected from published reports and calculated from corrosion product data (sample mass gain or corrosion product thickness) and tabulated for 75 alloys exposed to temperatures between ~800 and 2000 K (~500–1700 °C; 900–3000°F). Data were collected for environments including lab air, ambient and supercritical carbon dioxide, supercritical water, and steam. Materials studied include low- and high-Cr ferritic and austenitic steels, nickel superalloys, and aluminide materials. A combination of Arrhenius analysis, simple linear regression, supervised and unsupervised machine learning methods were used to investigate the relations between composition and oxidation kinetics. The supervised machine learning techniques produced the lowest mean standard errors. The most significant elements controlling oxidation kinetics were Ni, Cr, Al, and Fe, with Mo and Co composition also found to be significant features. The activation energies produced from the machine learning analysis were in the correct distributions for the diffusion constants for the oxide scales expected to dominate in each class.
Ni-based superalloys offer a unique combination of mechanical properties, corrosion resistance and high temperature performance. Near ambient pressure X-ray photoelectron spectroscopy was used to study in operando the initial steps of oxidation for Ni-5Cr, Ni-15Cr, Ni-30Cr and Ni-15Cr-6W at 500 °C, p(O 2 )=10 -6 mbar. The comparison of oxide evolution for these alloys quantifies the outsized impact of W in promoting chromia formation. For the binary alloys an increase in chromia due to Cr-surface enrichment is followed by NiO nucleation and growth thus seeding a dual-layer structure. The addition of W (Ni-15Cr-6W) shifts the reaction pathways towards chromia thus enhancing oxide quality. Density functional theory calculations confirm that W atoms adjacent to Cr create highly favorable oxygen adsorption sites. The addition of W supercharges the reactivity of Cr with oxygen essentially funneling oxygen atoms into Cr sites. The experimental results are discussed in the context of surface composition, chemistry, reactant fluxes, and microstructure.
A mechanism of Ni redeposition during dealloying corrosion of Ni-Cr is investigated. A model Ni20Cr (wt%) metal alloy was exposed to molten LiF-NaF-KF eutectic (FLiNaK) at 600 °C and at an applied potential of +2.1 VK+/K, above the critical potential for onset of dealloying. Upon extended exposure times (up to 12 h), prominent salt-filled corrosion channels emerge along grain boundaries. A unique grain boundary corrosion mechanism, with respect to the exposed faces of the grains, a central focus of this investigation, is intrinsically connected to the formation of high purity Ni-rich de-alloyed regions within the salt-filled channel. We implement microscale techniques such as energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD) to uncover morphological and compositional variations in relevance to the formation of bicontinuous porosity from corrosion dealloying. To rationalize our findings, a phase-field model is developed and discovers a mechanism in which dissolved Ni from one grain can be redeposited on an adjacent grain at a given difference in interfacial energies. The interaction of chemical and structural factors at the grain boundaries plays a central role in elucidating the dynamics of this phenomenon and its implications towards corrosion.
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Recent progress in the development of copper-alloy catalysts is highlighted, focusing on the structural and mechanistic characterizations of the catalysts in different catalytic reactions, and challenges and opportunities in future research.