Al x CoCrFeNi High Entropy Alloys (HEAs), also referred to as multiprincipal element alloys, have attracted significant interest due to their promising mechanical and structural properties. Despite these attributes, Al x CoCrFeNi HEAs are susceptible to phase separation, forming a wide range of secondary phases upon aging, including NiAl–B2 and Cr-rich phases. Controlling the formation of these phases will enable the design of age-hardenable alloys with optimized corrosion resistance. In this study, we examine the critical role of Al additions and their concentration on the stability of the CoCrFeNi base alloy, uncovering the connections between Al composition and the resulting microstructure. Addition of 0.1 mol fraction of Al destabilizes the single-phase microstructure and results in the formation of Cr-rich body-centered-cubic (bcc) phases. Increasing the composition of Al (0.3–0.5 mol fraction) results in the formation of more complex coprecipitates, NiAl–B2 and Cr-rich bcc. Interestingly, we find that the increase of the Al content stimulates the formation of NiAl–B2 phases, increases the overall density of secondary phases, and influences the content of Cr in Cr-rich bcc phases. Density functional theory calculations of simple decomposition reactions of Al x CoCrFeNi HEAs corroborate the tendency for precipitate formation of these phases upon increased Al composition. Additionally, these calculations support previous results, indicating the base CoCrFeNi alloy to be unstable at low temperature. This work provides a foundation for predictive understanding of phase evolution, opening the window toward designing innovative alloys for targeted applications.
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Influence of gaseous atmosphere on electrochemical behavior of nickel alloys in LiCl-KCl-Na2SO4 at 700 °C
Electrochemical behavior of Ni alloys (Ni, β-NiAl, β-NiAl/Cr) was investigated in LiCl-KCl-Na2SO4 electrolyte at 700 °C under three gaseous atmospheres (Ar, O2, O2-0.1%SO2). In oxidizing atmospheres, Ni rapidly degraded due to instability of NiO, and alumina-rich scale on β-NiAl provided limited protection against hot corrosion (e.g., cracks in the scale under O2-0.1%SO2); however, the addition of both Al and Cr resulted in enhanced corrosion resistance by forming a mixed-oxide (Al2O3-Cr2O3) scale in oxidizing atmospheres. In hot corrosion processes of Ni alloys, the formation and stability of oxide scales in the molten salt were influenced by gaseous atmosphere and alloying elements.
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- Award ID(s):
- 1662817
- NSF-PAR ID:
- 10095426
- Date Published:
- Journal Name:
- Corrosion science
- Volume:
- 142
- ISSN:
- 0010-938X
- Page Range / eLocation ID:
- 1-11
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Elemental partitioning during thermal processing can significantly affect the corrosion resistance of bulk alloys operating in aggressive electrochemical environments, for which, despite decades of experimental and theoretical studies, the thermodynamic and electrochemical mechanisms still lack accurate quantitative descriptions. Here, we formulate an ab initio thermodynamic model to obtain the composition- and temperature-dependent free energies of formation (Δf
G ) for Ni–Cr alloys, a prototypical group of corrosion-resistant metals, and discover two equilibrium states that produce the driving forces for the elemental partitioning in Ni–Cr. The results are in quantitative agreement with the experimental studies on the thermodynamic stability of Ni–Cr. We further construct electrochemical (potential–pH) diagrams by obtaining the required ΔfG values of native oxides and (oxy)hydroxides using high-fidelity ab-initio calculations that include exact electronic exchange and phononic contributions. We then analyze the passivation and electrochemical trends of Ni–Cr alloys, which closely explain various oxide-film growth and corrosion behaviors observed on alloy surfaces. We finally determine the optimal Cr content range of 14–34 at%, which provides the Ni–Cr alloys with both the preferred heat-treatment stability and superior corrosion resistance. We conclude by discussing the consequences of these findings on other Ni–Cr alloys with more complex additives, which can guide the further optimization of industrial Ni–Cr-based alloys. -
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Exposure testing was performed on CoCrFeMnNi equiatomic high entropy alloy (HEA) produced via directed energy deposition additive manufacturing in NaNO3-KNO3(60–40 wt%) molten salt at 500 °C for 50 h to evaluate the corrosion performance and oxide film chemistry of the HEA. Potentiodynamic electrochemical corrosion testing, scanning electron microscopy, focused ion beam milling coupled with energy dispersive spectroscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectroscopy were used to analyze the corrosion behavior and chemistry of the HEA/nitrate molten salt system. The CoCrFeMnNi HEA exhibited a higher passive current density during potentiodynamic polarization testing than steel alloys SS316L and 4130 and the high-Ni alloy 800 H in identical conditions. The oxide film was primarily composed of a (Mn,Co,Ni)Fe2O4spinel with a vertical plate-like morphology at the surface. Cr and Ni were found to be totally depleted at the outer surface of the oxide and dissolved in high concentrations in the molten salt. While Cr was expected to dissolve into the molten salt, the high concentration of dissolved Ni has not been observed with traditional alloys, suggesting that Ni is less stable in the spinel when Mn and Co are present.
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Abstract 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.more » « less
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Nickel-chromium-molybdenum (NiCrMo) alloys are well-known for having exceptional corrosion resistance, but their electrocatalytic properties have not been extensively studied. In this paper, the development of electro-active nickel-oxyhydroxide (NiOOH) phases and kinetics of the oxygen evolution reaction (OER) have been examined on alloys G35, B3, and C276 in alkaline electrolyte at 25 °C. Reproducible oxide layers were grown by potential cycling between 0.85 and 1.52 V vs RHE up to 600 cycles, and the transition between Ni(OH) 2 and NiOOH was monitored by cyclic voltammetry throughout. Onset potentials, Tafel slopes, and turnover frequencies (TOF) were measured at OER overpotentials between 270 and 390 mV. Alloys with dissimilar Cr:Mo ratios had significantly higher electrochemical surface area and increased γ -NiOOH formation, suggesting higher metal dissolution rates. The equal Cr:Mo concentration alloy and pure Ni developed a primarily β -NiOOH surface, and had 1.8–2.0 times larger TOF values than those containing significant γ -NiOOH. The NiCrMo alloys required smaller overpotentials (54–80 mV) to produce 10 mA cm −2 of OER current, and had comparable Tafel slopes to pure Ni. The findings here indicate a β -NiOOH-developed surface to be more OER-active than a γ -NiOOH-developed surface, and suggest certain NiCrMo alloys have promise as OER electrocatalysts.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.corsci.2018.05.039
