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1. Elemental partitioning and corrosion resistance of Ni–Cr alloys revealed by accurate ab-initio thermodynamic and electrochemical calculations

   https://doi.org/10.1038/s41529-023-00414-w  

   Huang, Liang-Feng; Xie, Yusi; Sieradzki, Karl; Rondinelli, James M. (December 2023, npj Materials Degradation)

   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 (Δ_fG) 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 Δ_fGvalues 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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2. Interaction of molecular nitrogen with vanadium oxide in the absence and presence of water vapor at room temperature: Near-ambient pressure XPS

   https://doi.org/10.1063/5.0107678  

   Balogun, K.; Chukwunenye, P.; Anwar, F.; Ganesan, A.; Adesope, Q.; Willadsen, D.; Nemšák, S.; Cundari, T. R.; Bagus, P. S.; D’Souza, F.; et al (September 2022, The Journal of Chemical Physics)

   Interactions of N2 at oxide surfaces are important for understanding electrocatalytic nitrogen reduction reaction (NRR) mechanisms. Interactions of N2 at the polycrystalline vanadium oxide/vapor interface were monitored at room temperature and total pressures up to 10−1 Torr using Near-Ambient Pressure X-ray Photoelectron Spectroscopy (NAP-XPS). The oxide film was predominantly V(IV), with V(III) and V(V) components. XPS spectra were acquired in environments of both pure N2 and equal pressures of N2 and H2O vapor. In pure N2, broad, partially resolved N1s features were observed at binding energies of 401.0 and 398.7 eV, with a relative intensity of ∼3:1, respectively. These features remained upon subsequent pumpdown to 10−9 Torr. The observed maximum N surface coverage was ∼1.5 × 1013 cm−2—a fraction of a monolayer. In the presence of equal pressures of H2O, the adsorbed N intensity at 10−1 Torr is ∼25% of that observed in the absence of H2O. The formation of molecularly adsorbed H2O was also observed. Density functional theory-based calculations suggest favorable absorption energies for N2 bonding to both V(IV) and V(III) cation sites but less so for V(V) sites. Hartree–Fock-based cluster calculations for N2–V end-on adsorption show that experimental XPS doublet features are consistent with the calculated shake-up and normal, final ionic configurations for N2 end-on bonding to V(III) sites but not V(IV) sites. The XPS spectra of vanadium oxide transferred in situ between electrochemical and UHV environments indicate that the oxide surfaces studied here are stable upon exposure to the electrolyte under NRR-relevant conditions. 

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3. Unraveling the role of tungsten as a minor alloying element in the oxidation NiCr alloys

   https://doi.org/10.1038/s41529-022-00265-x  

   Volders, Cameron; Angelici, Valentina Avincola; Waluyo, Iradwikanari; Hunt, Adrian; Árnadóttir, Líney; Reinke, Petra (December 2022, npj Materials Degradation)

   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. 

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4. Influence of gaseous atmosphere on electrochemical behavior of nickel alloys in LiCl-KCl-Na2SO4 at 700 °C

   https://doi.org/10.1016/j.corsci.2018.05.039  

   Kumar, Kuldeep; Gesualdi, Jarrod; Smith, Nathan; Kim, Hojong (May 2018, Corrosion science)

   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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5. Corrosion behavior of an in situ consolidated nanocrystalline Al-V alloy

   https://doi.org/10.1038/s41529-022-00225-5  

   Witharamage, C. S.; Christudasjustus, J.; Smith, J.; Gao, W.; Gupta, R. K. (February 2022, npj Materials Degradation)

   Abstract Supersaturated solid solutions of Al and corrosion-resistant alloying elements (M: V, Mo, Cr, Ti, Nb), produced by non-equilibrium processing techniques, have been reported to exhibit high corrosion resistance and strength. The corrosion mechanism for such improved corrosion performance has not been well understood. We present a fundamental understanding of the role of V in corrosion of an Al-V alloy, which will provide a theoretical background for developing corrosion-resistant Al alloys. High-energy ball milling of the elemental powder of Al and V produced an in situ consolidated Al-V alloy, which exhibited high solid solubility of V. The corrosion resistance of Al-V alloy was significantly higher than that of pure Al, which was attributed to the (1) enrichment of V at the passive film/substrate interface, (2) incorporation of V into the passive film, and (3) deposition of V on the iron-containing cathodic particles and therefore, retardation of cathodic reaction. 

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