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At least 415 records · Page 23

Engineering the electronic and strained interface for high activity of PdM core @Pt monolayer electrocatalysts for oxygen reduction reaction

Alloyed nanoparticles with core-shell structures provide a favorable model to modulate interfacial interaction and surface structures at the atomic level, which is important for designing electrocatalysts with high activity and durability. Herein, core-shell structured Pd 3 M@Pt/C nanoparticles with binary PdM alloy cores (M = Fe, Ni, and Co) and a monolayer Pt shell were successfully synthesized with diverse interfaces. Among these, Pd 3 Fe@Pt/C exhibited the best oxygen reduction reaction catalytic performance, roughly 5.4 times more than that of the commercial Pt/C catalyst used as reference. The significantly enhanced activity is attributed to the combined effects of strain engineering, interfacial electron transfer, and improved Pt utilization. Density functional theory simulations and extended X-ray absorption fine structure analysis revealed that engineering the alloy core with moderate lattice mismatch and alloy composition (Pd 3 Fe) optimizes the surface oxygen adsorption energy, thereby rendering excellent electrocatalytic activity. Finally, future researches may use this study as a guide on the construction of highly effective core-shell electrocatalysts for various energy conversions and other applications.

25 ENERGY STORAGE↗

The formation and evolution of Ni 2 Cr precipitates in Ni–Cr model alloys as a function of stoichiometry characterized by synchrotron x-ray diffraction

Ni-based alloys containing significant amounts of Cr, may precipitate new phases during long-term service at elevated temperatures. In Ni–Cr model alloys, the formation of Ni 2 Cr has been found to impact the material properties, including the strength and ductility after isothermal aging below the critical temperature of 590°C. In this work, we quantify the formation and evolution of long-range ordering in four Ni–Cr binary model alloys (Ni/Cr = 1.8, 2.0, 2.2, 2.4) after isothermal aging up to 10,000h at temperatures between 373 and 475°C. The alloys were characterized by hardness testing and synchrotron-based x-ray diffraction to quantify the impact of Ni 2 Cr phase fraction and precipitate size on mechanical properties. After 500h of isothermal aging, the formation of Ni 2 Cr was detected in all four alloys at 475°C. In the stochiometric alloy samples (Ni/Cr = 2.0), the formation of Ni 2 Cr was found after 500 and 3000h aging at 418 and 373°C, respectively. We found that the matrix lattice contraction and Ni 2 Cr phase fraction both saturate after early aging times. This is in stark contrast to the hardness and Ni 2 Cr precipitate size that both continue to increase with increasing aging time. Our results highlight that changes in hardness correlate linearly with Ni 2 Cr precipitate size rather than phase fraction. This important structure-property relationship can potentially help define Ni–Cr-based component lifetimes directly through an understanding of how Ni 2 Cr formation impacts strength and ductility. Here, we find that a precipitation hardening model for critical resolved shear stress with weakly coupled dislocations shows good agreement with the material property changes quantified from experimental measurements.

36 MATERIALS SCIENCE↗

Medium-range order and compositional correlation in metallic glasses

The compositional atomic ordering in metallic glasses was studied by simulation focusing on the medium-range order (MRO). Many metallic alloy liquids and glasses show MRO characterized by the oscillations in the atomic pair-distribution function (PDF) beyond the first peak, which decay exponentially with distance. To study the effects of the local chemical order on MRO, we examine the compositionally resolved PDF and its MRO for models of various binary metallic alloy glasses. We show that compositional ordering is limited mostly to the nearest-neighbor atoms and the MRO is largely independent of the compositional order. For some elements that strongly repel each other in the alloy, a second MRO periodicity is observed owing to the distinct correlations among them. These results are discussed in light of the idea that the MRO oscillations in the PDF describe the correlations in the atomic density fluctuations, rather than the detailed local atomic structure.

Atomic structure↗

Effective pair potential for random fcc CoCrFeMnNi alloys

The single-phase equiatomic CoCrFeMnNi alloy is a random solid solution of five elements on the face-centered cubic lattice, whose pure constituents crystallize in very different structures and exhibit diverse magnetic properties. Due to the randomness of the alloy, 80% of nearest neighbor bonds are between unlike elements and thus the details of bonding in pure structures are less important. The elastic moduli of this alloy give rise to small Cauchy pressure C 12 - C 44 , which suggests that the dominant part of bonding may be described by a simple pair potential. We test this hypothesis by developing a long-range Lennard-Jones potential in which the equilibrium crystal structures of pure constituents are taken as reference. The standard mixing rules for regular solutions are then adopted to obtain parameters for bonds between unlike elements in the quinary system. The transferability of this potential to quaternary CoCrFeNi, ternary CoCrNi, and binary FeNi alloys is investigated and the predictions compared with experiments and density functional theory calculations. By sampling over a large number of random configurations, we investigate the effect of compositional randomness on misfit volumes, energies of point defects and stacking faults, and the dislocation friction stresses experienced by moving edge and screw dislocations.

Materials Science↗

Deconvoluting the Effect of Chromium and Aluminum on the Radiation Response of Wrought FeCrAl Alloys After Low-Dose Neutron Irradiation

FeCrAl alloys have been extensively investigated over the past decade as a candidate material for accident-tolerant fuel cladding in light water reactors. Here, we have completed a first of its kind study where Al and Cr concentrations are varied systematically under neutron irradiation to elucidate the post irradiation microstructural and mechanical response as a direct result of alloying content. Neutron irradiations were performed on alloys with composition Fe-(10-13)Cr-(5-7)Al in wt.% at temperatures of 214, 357, and 557°C to a dose of ~1.8 dpa (displacements per atom). Dislocation loop sizes and dispersion characteristics did not show strong compositional dependence. However, there were noticeable effects of composition on the dispersion of Cr-rich α'-precipitates, particularly a decrease in number density with increasing Al content or a decrease in Cr content. The present results confirm previous studies indicating the Cr concentration in these precipitates is lower than that expected in binary FeCr alloys and that Al can act as a destabilizing alloying element for the deleterious α'-phase.

36 MATERIALS SCIENCE↗

Heterogenous activation of dynamic recrystallization and twinning during friction stir processing of a Cu-4Nb alloy

An interplay between high degree of shear deformation and deformation-induced heating occurs during friction stir processing (FSP) of metals. In medium-to-low stacking fault energy Cu alloys, this can lead to a complex spatially heterogenous activation of dynamic recrystallization (DRX) and twinning mechanisms. Within the Cu-Nb system, the presence of Nb is further expected to influence the DRX mechanism of the Cu matrix. However, the microstructural changes induced by the co-deformation of Nb during FSP are still not well understood. So, this study uses a combination of multimodal microstructural characterization, solution thermodynamics-based predictions, and computational crystal plasticity simulation to reveal the various microstructural evolution mechanisms that can occur during FSP of a Cu-4at.%Nb binary model alloy. The formation of softer DRX zones, and harder shear localization regions are revealed using electron backscatter diffraction, transmission electron microscopy, atom probe tomography, and crystal plasticity modeling.

36 MATERIALS SCIENCE↗

Hypereutectic Al-Ce-X (X=Mn, Cr, V, Mo, W) alloys fabricated by laser powder-bed fusion

Here, we characterize the microstructures and high-temperature mechanical properties of Al-2Ce and ternary Al-2Ce-1X (at.%) alloys fabricated by laser powder-bed fusion (LPBF), where X = Mn, Cr, V, Mo, and W are slow-diffusing transition metals. All ternary alloys show a hypereutectic microstructure in the as-LPBF state, containing an interconnected network of eutectic Al 11 Ce 3 phases (~10 vol.%) and an additional population of submicron, equiaxed Al 20 CeX 2 primary precipitates (~10 vol.%) which are isomorphous among these five alloys. Similar microstructures are present in arc-melted rods and atomized powders but are coarser due to the slower cooling rates in these processes. The hardness of the as-LPBF ternary Al-Ce-X alloys (1300–1400 MPa) is higher than that of the binary Al-Ce alloy (~1100 MPa) due to the higher volume fraction of strengthening phases. Furthermore, during exposure at 400 °C for up to three months, greater hardness retention is achieved in the ternary Al-Ce-X alloys (65–75%) than in the binary Al-Ce alloy (~55%), which is attributed to the extreme coarsening resistance of the Al 20 CeX 2 precipitates imparted by the very slow-diffusing ternary solute. These coarsening-resistant Al 20 CeX 2 precipitates also substantially improve alloy creep resistance, increasing the threshold stress for dislocation creep at 300°C from ~32 MPa for the binary Al-Ce alloy to ~77–100 MPa for the ternary Al-Ce-X alloys, and at 400°C from <10 MPa for the binary Al-Ce alloy to >40 MPa for the ternary Al-Ce-V alloy.

36 MATERIALS SCIENCE↗

Microstructural evolution in Cu-Nb processed via friction consolidation

Immiscible alloys, whether in well-mixed or layered forms, are of increasing interest based on their novel structural and functional properties, such as enhanced thermal stability against grain growth or radiation-induced defect trapping at the interfaces. To address the need for new approaches to tailor microstructures, the microstructural development of an immiscible Cu-Nb alloy processed via friction consolidation of elemental powders is investigated. Friction consolidation is a solid-phase processing technique that imparts severe plastic strain into a deforming volume resulting in elevated temperatures below the melting temperature of the alloy. Two distinct processing pathways were chosen to understand the effect of thermomechanical conditions on the final microstructure. The microstructure was characterized using scanning electron microscopy, scanning transmission electron microscopy, and X-ray diffraction techniques. Path 1 exhibited larger strain, strain rate, and temperature as compared with path 2. In path 1, agglomerated Nb particles were present in the recrystallized ultrafine-grained Cu matrix, while in path 2 extremely fine and dispersed Nb particles were present in a highly deformed Cu matrix. In both pathways, supersaturation of Cu in Nb lattices was noted, but not vice-versa. The asymmetry in mixing is explained based on deformation-based, thermodynamic and kinetic factors. These findings provide a pathway for creation of novel tailored microstructures and improved properties in any number of binary immiscible alloy systems.

Cu-Nb alloys, Microstructural refinement, Friction↗

Advanced eLectrical Bus (ALBus) CubeSat: From Build to Flight

Advanced eLectrical Bus (ALBus) CubeSat is a technology demonstration mission of a 3-U CubeSat with an advanced digitally controlled electrical power system and novel use of Shape Memory Alloy (SMA) technology for reliable deployable solar array mechanisms. The primary objective was to advance the power management and distribution (PMAD) capabilities to enable future missions requiring more flexible and reliable power systems with higher output power capabilities. Goals included demonstration of 100W distribution to a target electrical load, response to continuous and fast transient power requirements, and exhibition of reliable deployment of solar arrays and antennas utilizing re-settable SMA mechanisms. The power distribution function of the ALBus PMAD system is unique in the total power to target load capability, as power is distributed from batteries to provide 100W of power directly to a resistive load. The deployable solar arrays utilize NASA’s Nickel-Titanium-Palladium-Platinum (NiTiPdPt) high-temperature SMAs for the retention and release mechanism, and a superelastic binary NiTi alloy for the hinge component. The project launched as part of the CubeSat Launch Initiative (CLI) Educational Launch of Nanosatellites (ELaNa) XIX mission on Rocket Lab’s Electron in December 2018. This paper summarizes the final launched design and the lessons learned from build to flight.

Deboshri Sadhukhan↗

Advanced eLectrical Bus (ALBus) CubeSat: From Build to Flight

The Advanced eLectrical Bus (ALBus) CubeSat project is a technology demonstration mission of a 3-U CubeSat with an advanced, digitally controlled electrical power system capability and novel use of Shape Memory Alloy (SMA) technology for reliable deployable solar array mechanisms. The objective of the project was to advance the state of power management and distribution (PMAD) capabilities to enable future missions requiring flexible and reliable power systems with higher output power capabilities. The goals of the mission were to demonstrate 100W distribution to a target electrical load, respond to continuous and fast transient power requirements, and show reliable deployment of solar arrays and antennas utilizing re-settable SMA mechanisms. The power distribution function of the ALBus PMAD system is unique in the total power to target load capability. Power is distributed from batteries to provide 100W of power directly to a resistive load. The deployable solar arrays utilize NASA Glenn Research Center’s Nickel-Titanium-Palladium-Platinum high-temperature SMAs for the retention and release mechanism, and a super-elastic binary NiTi alloy for the hinge component. The deployable solar array hinge design features the utilization of SMA material properties for a dual purpose. First, the hinge uses the super-elastic SMA properties to provide the spring force to deploy the arrays. Second, the electrical conductivity properties of the SMA enables the design to provide clean conduits for power transfer from the deployable arrays to the power management system. This eliminates the need for electrical harnesses between the arrays and the PMAD system in the ALBus system design. The uniqueness of the SMA retention and release mechanism design is the ability to reset the mechanism and reuse the same hardware. This allow functional tests of the mechanisms before flight with no degradation of performance and flying the hardware that is tested. The project launched as part of the CubeSat Launch Initiative Educational Launch of Nanosatellites (ELaNa) XIX mission on Rocket Lab’s Electron in December 2018. This paper summarizes the final launched design of ALBus and lessons learned from the technology and overall project from development through flight.

Deboshri Sadhukhan↗

Influence of silicon on friction and wear of iron-cobalt alloys

Sliding friction and wear experiments were conducted with ternary ordered alloys of iron and cobalt containing various amounts of silicon to 5 weight percent. The friction and wear of these alloys were compared to those for binary iron-cobalt alloys in the ordered and disordered states and to those for the conventionally used bearing material, 440-C. Environments in which experiments were conducted included air, argon, and 0.25percent stearic acid in hexadecane. Results indicate that a ternary iron - cobalt - 5-percent-silicon alloy exhibits lower friction and wear than the simple binary iron-cobalt alloy. It exhibits lower wear than 440-C in all three environments. Friction was lower for the alloy in argon than in air. Auger analysis of the surface of the ternary alloy indicated segregation of silicon at the surface as a result of sliding.

Buckley, D. H.↗

Overcoming Anode Instability in Solid‐State Batteries through Control of the Lithium Metal Microstructure

Abstract Enabling the lithium metal anode (LMA) in solid‐state batteries (SSBs) is the key to developing high energy density battery technologies. However, maintaining a stable electrode–electrolyte interface presents a critical challenge to high cycling rate and prolonged cycle life. One such issue is the interfacial pore formation in LMA during stripping. To overcome this, either higher stack pressure or binary lithium alloy anodes are used. Herein, it is shown that fine‐grained ( d = 20 µm) polycrystalline LMA can avoid pore formation by exploiting the microstructural dependence of the creep rates. In a symmetric cell set‐up, i.e., LiǀLi 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZO)ǀLi, fine‐grained LMA achieves > 11.0 mAh cm −2 compared to ≈ 3.6 mAh cm −2 for coarse‐grained LMA ( d = 295 µm) at 0.1 mA cm −2 and at moderate stress of 2.0 MPa. Smaller diffusion lengths (≈ 20 µm) and higher diffusivity pathway along dislocations ( D d ≈ 10 −7 cm 2 s −1 ), generated during cell fabrication, result in enhanced viscoplastic deformation in fine‐grained polycrystalline LMA. The electrochemical performances corroborate well with estimated creep rates. Thus, microstructural control of LMA can significantly reduce the required stack pressure during stripping. These results are particularly relevant for “anode‐free” SSBs wherein both the microstructure and the mechanical state of the lithium are critical parameters.

25 ENERGY STORAGE↗

Kinetic study of Ni-M/CNT catalyst in methane decomposition under microwave irradiation

Methane catalytic decomposition has been studied with catalysts that can attenuate the energy of electromagnetic waves to heat and drive the reaction. Herein, we report, for the first time, a comprehensive kinetic study of Ni-M (M=Pd, Cu, or Fe)-CNT catalysts under microwave irradiation. These binary metal alloy nanoparticles have been synthesized on multiwalled carbon nanotube support with solvothermal process. These catalysts showed incredible performance for both absorbing microwave energy and catalyzing the reaction to form carbon nanotubes and hydrogen. Ni-M-CNT has a reaction order of 0.74. 10Ni-1 Pd-CNT, 10Ni-1Cu-CNT, and 10Ni-1Fe-CNT have activation energies at 87, 75, and 69 kJ/mol. The investigation was carried out in a differential reactor. The results indicated that 10Ni-1Fe-CNT had the lowest activation energy due to the increase in microwave susceptibility. Here, this work pioneered the microwave catalytic methane decomposition field as well as paving the way for future electrification of CO x -free hydrogen production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Geometric control of magnetic domain morphology in electrodeposited Ni rich NiPt mesoscopic wires

In this paper, we study the electrodeposited Ni—Pt magnetic wires, exploring the mechanisms by which changes in geometry and composition influence the local magnetic structure. The samples were prepared by electrodeposition, their elemental composition was analyzed by energy dispersive X-ray spectroscopy, and phase analysis was carried out by an X-ray diffraction measurement. Magnetic force microscopy measurements, and magnetic force microscopy measurements in magnetic field were carried out to study the domain morphology of the prepared samples. Magnetization characteristics were measured via vibrating sample magnetometry mode of a superconducting quantum interference device. Here, the results were analyzed and compared with micromagnetic simulations. It is shown that a strong perpendicular magnetic anisotropy is responsible for the characteristic checkerboard-like surface magnetization patterns, which can be tuned by geometrical constriction and Ni content. Understanding these relationships provides insights into the design of magnetic materials with tailored properties for advanced applications, like magnetic sensors.

Binary alloy↗

Helium causing disappearance of a/2<111> dislocation loops in binary Fe-Cr ferritic alloys

In this work, single and dual-beam self-ion irradiations were performed at 500°C on ultra-high purity Fe14%Cr alloy to ~0.33 displacements-per-atom (dpa), and 0 or 3030 atomic-parts-per-million (appm) helium/dpa, respectively. Using transmission electron microscopy, we reveal that helium can drastically modify the dislocation loop Burgers vector in Fe-Cr alloys. Helium co-implantation caused complete disappearance of a/2<111> type dislocation loops, and the microstructure consisted of only a<100> loops. Conversely, a/2<111> type loops were predominant without He co-implantation. The total loop density remained largely unaffected. The results strikingly contrast literature asserting that helium stabilizes a/2<111> type loops in bcc Fe alloys, based on low temperature irradiations. Collectively analyzing the results with literature suggest that the small positive interaction between helium and self-interstitial atoms (SIA) in Fe predicted by atomistic simulations maybe insufficient to holistically explain the dislocation loop microstructure development in presence of helium. Helium-SIA positive binding inadvertently implies elevated a/2<111> loop fraction and higher loop densities that the present results contradict. Helium induced high cavity density causing a preferential loss of highly glissile <111> clusters, leaving the matrix saturated with <100> type clusters is proposed as a potential mechanism. Further, the in-situ irradiations combined with Burgers vector analysis strengthened the evidence of Cr-induced dislocation loop mobility reduction that appears to stabilize the a/2<111> type loops and causes higher loop densities in Fe-Cr alloys.

36 MATERIALS SCIENCE↗

Combinatorial screening of crystal structure in Ba-Sr-Mn-Ce perovskite oxides with ABO 3 stoichiometry

ABO 3 oxides with the perovskite-related structures are attracting significant interest due to their promising physical and chemical properties for many applications requiring tunable chemistry, including fuel cells, catalysis, and electrochemical water splitting. Here we report on the crystal structure of the entire family of perovskite oxides with ABO 3 stoichiometry, where A and B are Ba, Sr, Mn, Ce. Given the vast size of this chemically complex material system, exploration for stable perovskite-related structures with respect to its constituent elements and annealing temperature is performed by combinatorial pulsed laser deposition and spatially-resolved characterization of composition and structure. As a result of this high-throughput experimental study, we identify hexagonal perovskite-related polytypic transformation as a function of composition in the Ba 1-x Sr x MnO 3 oxides after annealing at different temperatures. Furthermore, a hexagonal perovskite-related polytype is observed in a narrow composition-temperature range of the Ba 1-x Sr x MnO 3 oxides. In contrast, a tetragonally-distorted perovskite is observed across a wider range of compositions and annealing temperatures in the Sr 1-x Ce x MnO 3 oxides. This structure stability is further enhanced along the Ba 1-x Sr x MnO 3 - Sr 1-x Ce x MnO 3 pseudo-binary tie-line at x=0.25 by increasing Ba-incorporation and annealing temperature. These results indicate that the BaCe x Mn 1-x O 3 - Sr 1-x Ce x MnO 3 pseudo-binary oxide alloys (solid solutions) with tetragonal perovskite structure and broad composition-temperature range of stability are promising candidates for thermochemical water splitting applications.

36 MATERIALS SCIENCE↗