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At least 955 records · Page 53

Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

Firdosy, Samad A.↗

A Compendium of Scale Surface Microstructures: Ni(pt)al Coatings Oxidized at 1150 C for 2000 1-h Cycles

The surface structure of scales formed on Ni(Pt)Al coatings was characterized by SEM/EDS/BSE in plan view. Two nominally identical {100} samples of aluminide coated CMSX4 single crystal were oxidized at 1150 C for 2000 1-h cycles and were found to produce somewhat disparate behavior. One sample, with less propensity for coating grain boundary ridge deformation, presented primarily alpha-Al2O3 scale structures, with minimal weight loss and spallation. The original scale structure, still retained over most of the sample, consisted of the classic theta-alpha transformation-induced ridge network structure, with approx. 25 nm crystallographic steps and terraces indicative of surface rearrangement to low energy alumina planes. The scale grain boundary ridges were often decorated with a fine, uniform distribution of (Hf,Ti)O2 particles. Another sample, producing steady state weight losses, exhibited much interfacial spallation and a complex assortment of different structures. Broad areas of interfacial spalling, crystallographically-faceted (Ni,Co)(Al,Cr)2O4 spinel, with an alpha-Al2O3 base scale, were the dominant features. Other regions exhibited nodular spinel grains, with fine or (Ta,Ti)-rich (rutile) particles decorating or interspersed with the spinel. While these features were consistent with a coating that presented more deformation at extruded grain boundaries, the root cause of the different behavior between the duplicate samples could not be conclusively identified.

Smialek, James L.↗

Experiments on Lunar Core Composition: Phase Equilibrium Analysis of A Multi-Element (Fe-Ni-S-C) System

Previous geochemical and geophysical experiments have proposed the presence of a small, metallic lunar core, but its composition is still being investigated. Knowledge of core composition can have a significant effect on understanding the thermal history of the Moon, the conditions surrounding the liquid-solid or liquid-liquid field, and siderophile element partitioning between mantle and core. However, experiments on complex bulk core compositions are very limited. One limitation comes from numerous studies that have only considered two or three element systems such as Fe-S or Fe-C, which do not supply a comprehensive understanding for complex systems such as Fe-Ni-S-Si-C. Recent geophysical data suggests the presence of up to 6% lighter elements. Reassessments of Apollo seismological analyses and samples have also shown the need to acquire more data for a broader range of pressures, temperatures, and compositions. This study considers a complex multi-element system (Fe-Ni-S-C) for a relevant pressure and temperature range to the Moon's core conditions.

Go, B. M.↗

Ni-Ti Alloys for Aerospace Bearing Applications

Nickel-rich Ni-Ti alloys are emerging candidate materials for aerospace bearing applications. These alloys exhibit a unique combination of physical, chemical, and tribological properties that are highly relevant to challenging aerospace bearings and other mechanical components. Despite being made solely from metals, Ni-Ti alloys are classified as intermetallics with properties akin to both metals and ceramics. For instance, like metals, they are electrically conductive but they tend to be brittle like ceramics. When properly processed, they have high hardness, low elastic modulus and an extensive elastic deformation range that imparts extraordinarily high resilience and resistance to denting. New alloy compositions enable simpler thermal processing and machining and intensive microstructural analyses have helped elucidate the materials science mechanisms governing hardness. In this paper, the application of state-of-art in NiTi alloys for aerospace bearings and mechanical components is explored. In addition to reviewing future trends and remaining challenges, the unique approaches and methods of tailoring bearing design to accommodate NiTis unique properties is discussed.

intermetallics↗

Effects of Cr and Nb alloying additions on high temperature creep deformation of Ni-based superalloys

Micro-twinning is the major creep deformation mechanism in Ni-based superalloys at temperatures above 700 °C. Recent experiments suggest that superlattice stacking faults y ' in phase may serve as the precursors to twin formation. Segregation of alloying elements to these precursors may have a significant effect on formation and extension of micro-twins. Using atomistic modeling we investigate and explain the effects of Cr and Nb alloying additions on these processes. We consider the experimentally obtained creep curves for several Ni-based superalloys with different elemental compositions and relate the observed trends to the simulation results presented in this study. Our results help to rationalize the experimentally observed puzzling effects of elemental composition of the alloy on creep resistance.

Valery V. Borovikov↗

Chemical looping conversion of CH4/CO2 to syngas on 5wt.%Ni@Ce0.6Zr0.4O2 catalyst: Impact of dynamic accumulation of surface carbon and oxygen vacancies

Syngas, a combination of carbon monoxide (CO) and hydrogen (H2), is a precursor to many chemicals and fuels, contributing to the billion-dollar global hydrocarbon industry. Chemical looping reforming (CLR) of the greenhouse gases methane (CH4) and carbon dioxide (CO2) allows for energy-efficient production of syngas. 5wt.% nickel (Ni) on ceria-zirconia (5wt%Ni@Ce0.6Zr0.4O2) mixed metal oxide catalyst was investigated here to explore pathways for enhanced syngas production on sustainable earth-abundant transition metal supported catalysts. The role of reduction-oxidation (redox) state of the catalyst, and carbon formation on the catalyst surface during chemical looping is explored to drive superior reaction kinetics, conversions, selectivity, and syngas ratios (H2/CO). The bulk and surface structure of the catalyst, along with carbon deposition features were characterized by electron microscopy, X-Ray diffraction, and ex situ Raman spectroscopy. The dynamic evolution of catalysts under CLR reaction conditions and the intrinsic reaction mechanisms were probed with in situ Raman spectroscopy, in situ Fourier transform spectroscopy, dynamic oxygen storage capacity (DOSC), and the Temporal Analysis of Products (TAP) reactor studies. Intrinsic kinetics of syngas production via CLR was correlated to the redox state of catalyst and the participation of nickel-catalyzed multiwalled carbon nanotube (CNT) growth, allowing enhanced CLR reaction performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Intergranular oxidation and oxygen transport in Ni-20Cr during exposure to model dry and wet oxidation environments

Selective oxidation is a critical component of the proposed internal oxidation mechanism of stress corrosion cracking (SCC) for Ni-based alloys in primary water reactor (PWR) operation. To isolate and study this process, the binary Ni-20Cr was exposed to pressurized water and a CO/CO2 gas mixture. In both environments, the oxygen potential was kept under the Ni/NiO line to stimulate penetrative intergranular attack. A combination of electron microscopy and atom probe tomography was used to study the nanometer-scale details of the passivation and penetrative intergranular oxidation processes at high-energy grain boundaries. Oxygen transport towards the terminating oxidation front is elucidated with dedicated usage of oxygen isotopic tracer exchange experiments to support classical theories of internal oxidation, revealing preferred oxygen transport paths were visualized with sub-nanometer resolution.

Weiser, Martin↗

Elucidating the corrosion mechanism of commercial Ni-based Superalloys in UCl3 containing-chloride Molten Salt Systems

Molten salt reactors (MSRs) have gained renewed interest, providing several advantages over their predecessors, including the capability to consume spent fuels, enhancing the environmental sustainability of the uranium fuel cycle. For example, molten chloride fast reactors (MCFRs) can reach criticality with molten chloride spent fuel containing high concentrations of impurities, such as actinide products like uranium chloride (UCl3). However, the redox potential of chloride molten salt fuels may change in the presence of these impurities, dictating their corrosivity and in turn the corrosion performance of structural components, such as those constructed from nickel (Ni)-based alloys. The purpose of this investigation is to assess the extent of corrosion of Ni-based alloy, Inconel 617, when exposed to UCl3-LiCl-KCl eutectic salt. Inconel 617 one of only six structural materials that are fully qualified by the American Society for Mechanical Engineers (ASME) Boiler and Pressure Vessel Code for high-temperature nuclear reactor components, making it a technologically mature material to consider for constructing MCFRs. Inconel 617 specimens were submerged in a static LiCl-KCl-UCl3 eutectic salt mixture heated at 700 C for 1000 h under an inert atmosphere. Upon completion, the extent of corrosion was analyzed through a multi-modal characterization approach spanning the engineering to nanoscale, employing computed tomography, focused-ion beam, and transmission electron microscopy techniques. Results from this investigation will enhance our understanding of property-to-performance relationships of candidate structural materials for MSRs with respect to corrosion resistance and interactions between the salt and alloy interface.

36 MATERIALS SCIENCE↗

Elucidating the corrosion mechanism of commercial Ni-based superalloys in UCl3 containing-chloride molten salt systems

Elucidating the role of UCl3 in the corrosion mechanism of Ni-based superalloys exposed to chloride molten salts Trishelle Copeland-Johnson1, Michael Woods1, Ruchi Gakhar1, Daniel J. Murray1, Guoping Cao1, Lingfeng He1 1Idaho National Laboratory, Idaho Falls, ID, United States The United States Department of Energy (DOE) aims to diversify the domestic energy portfolio towards more sustainable options, including implementation of molten salt reactor (MSR) technology. Chloride molten salts have been investigated as an appropriate MSR coolant and fuel because their relatively inexpensive, abundant, and exhibit favorable thermophysical properties. However, the corrosivity of chloride molten salts have not been extensively studied, especially with the inclusion of actinide products, such as UCl3. Accordingly, the development of nuclear structural materials with excellent corrosion performance is critical to the successful implementation of MSRs, particularly from a mechanistic perspective. In this investigation, we attempt to elucidate the interfacial corrosion mechanism between Ni-based structural materials, such as Inconel 617, and UCl3-containing salt systems through a multi-modal advanced characterization approach, including electron microscopy techniques. The findings from this investigation will expand the knowledgebase of chloride molten salt corrosion of MSR structural materials for strategic property-to-performance design.

36 - MATERIALS SCIENCE↗

Enabling Structure/Interface Regulation for High Performance Ni-Rich Cathodes

Here, further commercialization of Ni-rich layered cathodes is hindered by severe structure/interface degradation and kinetic hindrance that occur during electrochemical operation, which leads to safety risks and reduced range in electric vehicles (EVs). Herein, by selecting elements with different solubility properties, a multifunctional strategy that synchronously fabricates perovskite-type SrZrO 3 coating and Sr/Zr co-doping is employed to strengthen the structure/interface stability and the Li + transport mobility of LiNi 0.85 Co 0.10 Mn 0.05 O 2 (NCM). Perovskite-type SrZrO 3 protective layers formed on the particle surface can substantially mitigate the unexpected interfacial side reactions and surface phase transitions. In addition, a robust crystal framework is constructed by optimizing local O coordination through the introduction of strong Zr-O bonds. Notably, Li + diffusion kinetics is effectively improved due to expanded cell parameters and O-Li-O slab spacing with the incorporation of large-diameter Sr pillar ions, as revealed by X-ray diffraction. As a result, the Sr/Zr-modified NCM achieves a remarkable capacity retention of 99.4% after 200 cycles at 1 C, and a high rate capacity of 168.9 mAh g -1 at 10 C. This work opens new avenues to develop high-performance NCM cathodes with high energy and high power for EVs with long calendar life.

25 ENERGY STORAGE↗

Synergistic Effects of Molten Salt Corrosion and Proton Irradiation on Grain Boundary Strength in Ni-20Cr

Nickel-based alloys are leading contenders for use as structural materials in molten salt reactors. While there have been extensive studies on the impact of fluoride/chloride-based molten salt corrosion on the microstructural evolution of various nickel-based alloys, the effects of simultaneous molten salt corrosion and radiation on the mechanical integrity of grain boundaries (GBs) remain underexplored. In this study, we use a Ni-20Cr model alloy to investigate this issue, subjecting it to simultaneous molten fluoride salt corrosion and proton irradiation. We performed cross-sectional and chemically-sensitive electron microscopy characterization of the microstructures of these materials, identifying the characteristic corrosion-induced microstructure and local chemical heterogeneity near GBs. After developing a sample preparation method for reliable characterization of GB strength, we assess the mechanical degradation of GBs using in situ push-to-pull micro tensile tests. Our findings reveal that voids induced by corrosion are the primary influence on the failure mode of GBs, regardless of whether proton irradiation is present. For materials that exhibit ductile fracture, those subjected to simultaneous corrosion and radiation exhibit lower yield strengths than those exposed to corrosion alone, which may be linked to the previously observed phenomenon of proton irradiation-decelerated intergranular corrosion in molten salt.

36 - MATERIALS SCIENCE↗

Materials Data on Ni(AsO3)2 by Materials Project

NiAs2O6 is zeta iron carbide-derived structured and crystallizes in the trigonal P-31m space group. The structure is three-dimensional. Ni2+ is bonded to six equivalent O2- atoms to form NiO6 octahedra that share corners with twelve equivalent AsO6 octahedra. The corner-sharing octahedral tilt angles are 52°. All Ni–O bond lengths are 2.14 Å. As5+ is bonded to six equivalent O2- atoms to form AsO6 octahedra that share corners with six equivalent NiO6 octahedra and edges with three equivalent AsO6 octahedra. The corner-sharing octahedral tilt angles are 52°. All As–O bond lengths are 1.86 Å. O2- is bonded in a distorted trigonal planar geometry to one Ni2+ and two equivalent As5+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ni(AgO)2 by Materials Project

Ag2NiO2 is Calaverite-derived structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three Ag2NiO2 sheets oriented in the (0, 0, 1) direction. Ni2+ is bonded to six equivalent O2- atoms to form edge-sharing NiO6 octahedra. All Ni–O bond lengths are 2.06 Å. Ag1+ is bonded in a 3-coordinate geometry to three equivalent O2- atoms. All Ag–O bond lengths are 2.42 Å. O2- is bonded to three equivalent Ni2+ and three equivalent Ag1+ atoms to form a mixture of edge and corner-sharing ONi3Ag3 octahedra. The corner-sharing octahedral tilt angles are 0°.

36 MATERIALS SCIENCE↗

Materials Data on Ni(SbO3)2 by Materials Project

NiSb2O6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Ni2+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with eight equivalent SbO6 octahedra and edges with two equivalent SbO6 octahedra. The corner-sharing octahedral tilt angles are 51°. All Ni–O bond lengths are 2.07 Å. Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with four equivalent NiO6 octahedra, corners with four equivalent SbO6 octahedra, an edgeedge with one NiO6 octahedra, and an edgeedge with one SbO6 octahedra. The corner-sharing octahedra tilt angles range from 48–51°. There are two shorter (2.00 Å) and four longer (2.02 Å) Sb–O bond lengths. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to one Ni2+ and two equivalent Sb5+ atoms. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ni2+ and two equivalent Sb5+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ni(BMo)2 by Materials Project

Mo2NiB2 crystallizes in the orthorhombic Immm space group. The structure is three-dimensional. Mo2+ is bonded in a 6-coordinate geometry to six equivalent B3- atoms. There are four shorter (2.33 Å) and two longer (2.54 Å) Mo–B bond lengths. Ni2+ is bonded in a square co-planar geometry to four equivalent B3- atoms. All Ni–B bond lengths are 2.10 Å. B3- is bonded in a 9-coordinate geometry to six equivalent Mo2+, two equivalent Ni2+, and one B3- atom. The B–B bond length is 1.84 Å.

36 MATERIALS SCIENCE↗

Materials Data on Ni(CO)6 by Materials Project

Ni(C)2(CO)4O2 crystallizes in the monoclinic C2/c space group. The structure is zero-dimensional and consists of sixteen formaldehyde molecules, four hydrogen peroxide molecules, eight methane molecules, and four nickel molecules.

36 MATERIALS SCIENCE↗

Materials Data on Ni(N3O2)2 by Materials Project

NiO4N2(N2)2 is Cyanogen Chloride-derived structured and crystallizes in the monoclinic C2/m space group. The structure is zero-dimensional and consists of four nitrogen molecules and two NiO4N2 clusters. In each NiO4N2 cluster, Ni2+ is bonded in a linear geometry to two equivalent O2- atoms. Both Ni–O bond lengths are 2.02 Å. N1+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.22 Å) and one longer (1.29 Å) N–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Ni2+ and one N1+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one N1+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Ni(AsO2)2 by Materials Project

NiAs2O4 crystallizes in the tetragonal P4_2/mbc space group. The structure is three-dimensional. Ni2+ is bonded to six O2- atoms to form edge-sharing NiO6 octahedra. There are four shorter (2.04 Å) and two longer (2.14 Å) Ni–O bond lengths. As3+ is bonded in a 3-coordinate geometry to three O2- atoms. There is one shorter (1.76 Å) and two longer (1.89 Å) As–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Ni2+ and one As3+ atom. In the second O2- site, O2- is bonded in a trigonal planar geometry to one Ni2+ and two equivalent As3+ atoms.

36 MATERIALS SCIENCE↗