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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrochemical noise studies on localized corrosion of Ni and Ni-20Cr in molten ZnCl 2

The electrochemical noise (ECN) technique was employed to study corrosion of two model systems, i.e. pure Ni and a binary Ni-20 wt%Cr (Ni20Cr) alloy in molten ZnCl 2 at 623 K. Here we measured ECN transients in current and open-circuit potential from two nominally identical Ni-Ni and Ni20Cr-Ni20Cr electrodes and one galvanic Ni-Ni20Cr electrode pair. The behavior of ECN is quite distinct among the three-electrode systems, and it is correlated with the various microscopic observations of micro- and nano-scale morphological features. Based on the ECN study coupled with the microstructural analysis, the origins of ECN in the molten salt environment as well as the mechanisms of localized corrosion in the three systems are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Evolution of the Rate-Limiting step: From Thin Film to Thick Ni-rich Cathodes

Ni-rich NMC (LiNixMnyCo1-x-yO2, x = 0.6) has the attributes of high specific capacity (greater than 180 mAh g-1), high operating voltage (ca. 3.8 V) and low cost, which is therefore deemed as one of the most promising cathode candidates for next-generation high-energy Li-ion batteries (LIBs). However, challenges exist before the large-scale commercialization of Ni-rich cathode such as gas generation, capacity degradation especially at high rate or elevated temperatures. From thin film to densely pack high loading cathode, this work investigates the rate-limiting steps in Ni-rich cathodes e.g., phase structure, electronic and ionic conductivity to understand the reaction kinetics at different scales. This work provides new insights in understanding the electrochemical properties of Ni-rich cathode at different levels to inspire revolutionary ideas to address the fundamental issues of Ni-rich cathode from materials to relevant electrode levels.

Hu, Jiangtao↗
DOE OSTI2020

In situ investigation of the deformation behaviors of Fe 20 Co 30 Cr 25 Ni 25 and Fe 20 Co 30 Cr 30 Ni 20 high entropy alloys by high-energy X-ray diffraction

In situ synchrotron-based high-energy X-ray diffraction (HE-XRD) technique was employed to investigate the mechanical behaviors and microstructural evolution of face-centered cubic (FCC) Fe 20 Co 30 Cr 25 Ni 25 and Fe 20 Co 30 Cr 30 Ni 20 high entropy alloys (HEAs) during tensile deformation. Fe 20 Co 30 Cr 30 Ni 20 HEA has a good combination of strength (ultimate tensile strength of 864 ± 35 MPa) and ductility (elongation of 0.627 ± 0.021). The HE-XRD investigation reveals that Fe 20 Co 30 Cr 30 Ni 20 HEA has the transformation-induced plasticity (TRIP) effect, which starts at a critical stress of ~555 MPa. Furthermore, transmission electron microscopy confirmed this deformation-induced new phase is hexagonal-close-packed structured ε-martensite, which follows an orientation relationship of {111} γ //(0001) ε , and (110) γ //[11 2 ¯ 0] ε with the FCC γ matrix. The observation of deformation twins in the deformed samples of the two studied HEAs proves that twinning-induced plasticity (TWIP) effect occurs in both HEAs. The combination of TRIP and TWIP effects lead to the high strength, large ductility and improved strain hardening behavior of Fe 20 Co 30 Cr 30 Ni 20 HEA.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Density Functional Theory Study of the Adsorption and Dissociation of Copper(I) Acetamidinates on Ni(110): The Effect of the Substrate

In order to assess the role of a metal substrates on the thermal chemistry of adsorbed acetamidinate metalorganic compounds, we have studied the surface chemistry of copper(I)–N,N'-dimethylacetamidinate on Ni(110) using density functional theory and contrasted it with similar calculations we previously carried out on Cu(110). At low coverages, it was found that, in its most stable configuration, the molecular adsorption of copper(I)–N,N'-dimethylacetamidinate dimers occurs with the Cu atoms occupying surface hollow sites. In this work, the ligands reorient away from those metal centers, and the N atoms develop new direct bonds with surface Ni atoms. However, this configuration is not stable and decomposes by losing both ligands to the surface. In the final state, the two ligands bind via their N atoms to Ni sites one lattice space away from the sites where the Cu atoms remain, with their molecular planes perpendicular to that of the surface. This is in contrast with what happens in the case of adsorption on Cu(110), where the Cu atoms from the metalorganic complex still occupy hollow sites but where only one of the ligands breaks away and binds directly to the surface; the other remains on top of the two Cu ions. In terms of the energetics of adsorption and decomposition, the reactions on Ni(110) are much more exothermic than on Cu(110). Further analysis of the distribution of charge within the adsorbates shows a minor reduction of the Cu atoms of the dimer upon interaction with the surface; full reduction to metallic copper is complete only when both ligands have fully migrated to their new Ni surface sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Mixed Valence {Ni 2+ Ni 1+ } Clusters as Models of Acetyl Coenzyme A Synthase Intermediates

Acetyl coenzyme A synthase (ACS) catalyzes the formation and deconstruction of the key biological metabolite, acetyl coenzyme A (acetyl-CoA). The active site of ACS features a {NiNi} cluster bridged to a [Fe4S4] n+ cubane known as the A-cluster. The mechanism by which the A-cluster functions is debated, with few model complexes able to replicate the oxidation states, coordination features, or reactivity proposed in the catalytic cycle. In this work, we isolate the first bimetallic models of two hypothesized intermediates on the paramagnetic pathway of the ACS function. The heteroligated {Ni 2+ Ni 1+ } cluster, [K(12-crown-4) 2 ][1], effectively replicates the coordination number and oxidation state of the proposed “A red ” state of the A-cluster. Addition of carbon monoxide to [1] - allows for isolation of a dinuclear {Ni 2+ Ni 1+ (CO)} complex, [K(12-crown-2) n ][2] (n = 1–2), which bears similarity to the “A NiFeC ” enzyme intermediate. Structural and electronic properties of each cluster are elucidated by X-ray diffraction, nuclear magnetic resonance, cyclic voltammetry, and UV/vis and electron paramagnetic resonance spectroscopies, which are supplemented by density functional theory (DFT) calculations. Calculations indicate that the pseudo-T-shaped geometry of the three-coordinate nickel in [1] – is more stable than the Y-conformation by 22 kcal mol –1 , and that binding of CO to Ni 1+ is barrierless and exergonic by 6 kcal mol –1 . UV/vis absorption spectroscopy on [2] - in conjunction with time-dependent DFT calculations indicates that the square-planar nickel site is involved in electron transfer to the CO π*-orbital. Further, we demonstrate that [2] - promotes thioester synthesis in a reaction analogous to the production of acetyl coenzyme A by ACS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Atomic structure and melting of Ni and Fe 36 Ni up to 400 GPa

Iron, nickel and its alloys are critically important materials for industrial and technological applications due to their unique magnetic properties, strength, and thermal expansion. In this study, lasers were used to compress and heat Fe 36 Ni alloy (36 wt% Ni) and pure nickel up to the melting temperature using a combination of shock and ramp compression. The structure was measured using nanosecond in-situ x-ray diffraction, and simultaneous velocimetry was used to measure the pressure up to 454 GPa. A mixed face-centered-cubic (fcc) solid–liquid phase in Fe 36 Ni at 311 GPa provides experimental evidence that, compared to pure iron, the incorporation of nickel expands the stability field of the fcc phase to the melting curve. At lower temperatures, a mixed fcc and hexagonal-close-packed (hcp) phase is observed in ramp-compressed Fe 36 Ni at 278 GPa. At the higher compressions, a structure inconsistent with fcc, hcp, and body-centered cubic (bcc) is observed. In the case of pure Ni, the fcc phase is stable under ramp compression up to 402 GPa.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Electrochemical Study on the Kinetic Properties of Fe 2+ /Fe, Ni 2+ /Ni, Cr 2+ /Cr and Cr 3+ /Cr 2+ in Molten MgCl 2 -KCl-NaCl Salts

Here, the fundamental kinetic parameters of corrosion product ions (Fe, Ni and Cr ions) are of significant importance to understand the corrosion mechanisms of the structural materials in the molten salts. In the present study, the fundamental data of Fe 2+ , Ni 2+ , Cr 2+ and Cr 3+ (diffusion coefficient D, exchange current density i 0 , charge transfer coefficient α, limiting current density i L and standard rate constant k0) were measured at different concentrations (1.53 × 10 –6 –7.48 × 10 –4 mol cm –3 ) and temperatures (600 °C–800 °C). The values of D are independent of concentrations and follow Arrhenius law with temperature, which descend in the order of D Cr 2+ > D Fe 2+ > D Cr 3+ > D Ni 2+ with values ranging from 0.94 × 10 –5 to 3.31 × 10 –5 cm 2 s –1 . Both i 0 and k 0 depend on the temperatures, which also follow Arrhenius law.

14 SOLAR ENERGY↗
DOE OSTI2020

Structure and Behavior of the Ni End-Member Schreibersite Ni 3 P under Compression to 50 GPa

To better understand the potential presence of light element alloys of Fe and Ni in the Earth’s interior, the crystal structure and compressional behavior of the Ni-P binary compound, schreibersite (Ni 3 P), have been investigated using synchrotron X-ray diffraction experiments. Both powder and two single-crystal samples of synthetic Ni 3 P (in different orientations with respect to the loading axis of the diamond anvil cell) were compressed up to approximately 50 GPa at ambient temperature. The compressional data obtained for Ni3P were fitted with a 3rd order Birch–Murnaghan equation of state. All data indicated that the c/a ratio of unit cell parameters remained approximately constant up to about 30 GPa but then increased progressively with pressure, exhibiting a second slight discontinuity at approximately 40 GPa. The changes in unit cell parameters at ~30 GPa and ~40 GPa suggested discontinuous changes in magnetic ordering. Moreover, the threshold of these subtle discontinuities is sensitive to the stress state and orientation of the crystal in the diamond anvil cell. This study is the first report on the compressional behavior of both powder and single-crystal schreibersite at high-pressure (up to 50 GPa). It offers insights into the effects of Ni 3 P components on the compressional behavior of the Earth’s core.

36 MATERIALS SCIENCE↗
NASA NTRS1987

Interdiffusion in Ni-rich, Ni-Cr-Al alloys at 1100 and 1200 C. I - Diffusion paths and microstructures. II - Diffusion coefficients and predicted concentration profiles

Interdiffusion in Ni-rich Ni-Cr-Al alloys is investigated experimentally after annealing at 1100 and 1200 C using gamma/gamma, gamma/gamma+beta, gamma/gamma+gamma prime, and gamma/gamma+alpha diffusion couples. The amount and location of Kirkendall porosity suggests that Al diffuses more rapidly than Cr which diffuses more rapidly than Ni in the gamma phase of Ni-Cr-Al alloys. The location and extent of maxima and minima in the concentration profiles of the diffusion couples indicate that both cross-term diffusion coefficients are positive. Measurements are also presented of the ternary interdiffusion coefficients of the gamma phase in the Ni-Cr-Al system. It is shown that the interdiffusion coefficients can be accurately predicted by using a ternary finite-difference interdiffusion model.

Nesbitt, J. A.↗
DOE OSTI2025

Cu-induced robust Ni 2+ /Ni 3+ transition on amorphous Ni hydroxide-based electrocatalysts for advancing electrochemical ammonia oxidation and hydrogen evolution

The electrochemical ammonia oxidation reaction (AOR) is a promising anodic reaction for hydrogen production, offering a lower theoretical potential compared to oxygen evolution reaction. Despite this thermodynamic advantage, AOR suffers from sluggish multi-electron transfer reaction kinetics and the regeneration of catalytically active Ni 3+ species, which limits both activity and durability. In this study, amorphous NiCu bimetallic catalysts were prepared via facile precipitating metal nitrate deposition (PMND) method. The addition of Cu induces a robust Ni 2+ /Ni 3+ transition, stabilizing catalytically active Ni 3+ species and modulating the electronic structure of Ni. It alters the oxidation and desorption behavior of nitrogen-containing intermediates and facilitating their conversions to NO x species, resulting in fast active site regeneration. Furthermore, amorphous structure provides abundant dangling bonds, which enhances the intrinsic reactivity and accessibility of active sites rather than increasing the number of active sites. As a result, these effects accelerate the overall reaction kinetics. The optimized NiCu 5:1 catalyst achieved an ammonia removal efficiency of ∼100 % and a hydrogen production rate of 2.45 mmol/(h∙cm 2 ) at 1.6 V RHE .

Amorphous electrocatalyst↗
DOE OSTI2021

Mechanistic Insights into CO 2 Electroreduction on Ni 2 P: Understanding Its Selectivity toward Multicarbon Products

Recently, nickel phosphides (Ni x P y ) have been reported to enable selective electrochemical formation of multicarbon products (C 3 and C 4 ) via the CO 2 reduction reaction (CO 2 RR); nevertheless, their activities remain low. In order to understand the roots of their high selectivity and low activity and to direct the design of more active Ni x P y -based CO 2 RR catalysts, we investigate the CO 2 RR mechanism on Ni 2 P using density functional theory (DFT) calculations. Iin this work, we reveal that the reaction proceeds through the formate pathway, followed by formaldehyde (H 2 CO*) formation and self-condensation. Moreover, we demonstrate that surface hydride transfer steps, along with surface-mediated C–C coupling, are essential in order to avoid C 1 product formation and boost selectivity toward multicarbon products. In addition, we find that the thermal surface hydride transfer from the surface to the physisorbed CO 2 is one of the key rate-limiting steps, and since it is not electroactive, it cannot be accelerated by applying an overpotential. Finally, our results also show that the hydrogen affinity of the surface and the dynamic surface reconstruction via H adsorption facilitate selective CO 2 reduction and C–C coupling on Ni 2 P. These findings provide an impetus for exploring materials design space to identify the physical principles that govern the thermodynamics of rate-limiting thermal steps in electrocatalytic processes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The Application of Pulse Radiolysis to the Study of Ni(I) Intermediates in Ni-Catalyzed Cross-Coupling Reactions

Here we report the use of pulse radiolysis and spectroelectrochemistry to generate low-valent nickel intermediates relevant to synthetically important Ni-catalyzed cross-coupling reactions and interrogate their reactivities toward comproportionation and oxidative addition processes. Pulse radiolysis provided a direct means to generate singly reduced [(dtbbpy)NiBr], enabling the identification of a rapid Ni(0)/Ni(II) comproportionation process taking place under synthetically relevant electrolysis conditions. Furthermore, this approach also permitted the direct measurement of Ni(I) oxidative addition rates with electronically differentiated aryl iodide electrophiles (k OA = 1.3 × 10 4 –2.4 × 10 5 M –1 s –1 ), an elementary organometallic step often proposed in nickel-catalyzed cross-coupling reactions. Together, these results hold implications for a number of Ni-catalyzed cross-coupling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Uncovering the re-distribution mechanism of Ni in a de-alloyed Ni-Cr alloy in molten fluorinated salts

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.

Mills, Sean H↗
DOE OSTI2021

First direct measurement of 59 Cu(p,α) 56 Ni: A step towards constraining the Ni-Cu cycle in the cosmos

Reactions on proton-rich nuclides drive the nucleosynthesis in core collapse supernovae (CCSNe) and in x-ray bursts (XRBs). CCSNe eject the nucleosynthesis products to the interstellar medium and hence are a potential inventory of p nuclei, whereas in XRBs nucleosynthesis powers the light curves. In both astrophysical sites the Ni-Cu cycle, which features a competition between 59 Cu(p,α) 56 Ni and 59 Cu(p,γ) 60 Zn, could potentially halt the production of heavier elements. Here, we report the first direct measurement of 59 Cu(p,α) 56 Ni using a reaccelerated 59Cu beam and a cryogenic solid hydrogen target. Furthermore, our results show that the reaction proceeds predominantly to the ground state of 56 Ni, and the experimental rate has been found to be lower than Hauser-Feshbach based statistical model predictions. New results hints that the νp process could operate at higher temperatures than previously inferred and therefore remains a viable site for synthesizing the heavier elements

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Direct measurement of 59 Ni( n, p ) 59 Co and 59 Ni( n, α ) 56 Fe at fast-neutron energies from 500 keV to 10 MeV

We report nuclear reaction data for neutron induced reactions on unstable nuclei are critical for a wide range of applications spanning studies of nuclear astrophysics, nuclear reactor designs, and radiochemistry diagnostics. However, nuclear data evaluations of the reaction cross sections are largely based on calculations due to the difficulty in performing this class of measurements and the resulting lack of experimental data. For neutron induced charged particle reactions at fast neutron energies, at the MeV scale, these cross section predictions are predominately driven by statistical Hauser-Feshbach calculations. In this work, we present partial and total 59 Ni(n, p) and 59 Ni(n, α) cross sections, measured directly with a radioactive 59 Ni target, and compare the results to the present nuclear data evaluations. In addition, the results from this work are compared to a recent study of the 59 Ni(n, xp) reaction cross section that was performed via an indirect surrogate ratio method. The expected energy trend of the cross section, based on the current work, is inconsistent with that of the surrogate work. This calls into question the reliability of that application of the surrogate ratio method and highlights the need for direct measurements on unstable nuclei, when feasible.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Potential Dependent Mn Oxidation and Its Role in Passivation of Ni 38 Fe 20 Cr 22 Mn 10 Co 10 Multi-Principal Element Alloy Using Multi-Element Resolved Atomic Emission Spectroelectrochemistry

The identity of passivating oxides on multi-principal element alloys is of great interest as their optimization offers the potential for exceptional corrosion resistance in aqueous solutions over a broad range of potential and pH. This study focuses on a non-equiatomic Ni 38 Fe 20 Cr 22 Mn 10 Co 10 solid solution alloy and tracks the fate of each alloying element during linear sweep voltammetry, low and intermediate potential holds in the passive potential domain as well as during open circuit relaxation after anodic polarization in slightly acidified Cl − solution. Ni dissolves at all potentials investigated in this work, Fe and Co are incorporated into oxides or hydroxides in low concentrations whilst Cr and Mn are enriched at passive potentials. At low passivating potentials, Mn(II) dissolves and is incorporated in minor amounts in oxides containing large concentrations of Cr(III). Considerable enrichment in Mn(II)-species occurs relative to Cr(III) in the oxide at 0.1 V vs SCE. Electrochemical impedance spectroscopy suggests the presence of layered oxides with marginal passivation at high Mn(II) levels. The formation of these oxides depends on a combination of thermodynamic and kinetic factors as well as the sequence of passivation.

Han, Junsoo (ORCID:0000000192952954)↗