Structure of Chlorine K-Edge XANES Spectra During the Breakdown of Passive Oxide Films on Aluminum

O’Grady, W.E.; Roeper, Donald F.; Natishan, Paul M.

doi:10.1021/jp2056305

Cited by 26 publications

(21 citation statements)

References 25 publications

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“…The modeling work by O'Grady et al 79 show Cl − within the oxide and at the oxide metal/interface at potentials below E pit . These experimental and modeling data, in the view of the authors, present a very compelling case that Cl − is incorporated in the entirety of the oxide film at the potentials studied below and above E pit and that Cl − moves through the oxide film.…”

Section: Discussionmentioning

confidence: 99%

“…The The XANES data recorded at -0.850 V sce were compared to the theoretically calculated LDOS spectrum for four possible oxygen positions. 79 The theoretical LDOS for Cl − in the recessed site was compared with the XANES data shown in Figure 14. Of the 4 possibilities, this simulation yielded the best fit of the calculated spectrum with the actual data.…”

Section: Experimental Evidence For Chloride Incorporation In the Oxidmentioning

confidence: 99%

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Chloride Ion Interactions with Oxide-Covered Aluminum Leading to Pitting Corrosion: A Review

Natishan

O’Grady

2014

J. Electrochem. Soc.

238

122

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Metals and alloys such as aluminum (Al), stainless steels, and nickel-based alloys exhibit corrosion resistance in a wide range of environments due to the presence of protective, passive oxides. However, in environments that contain aggressive anions such as chloride, Cl − , the passive film becomes unstable and degrades locally causing film breakdown and pitting corrosion. A number of theories describing the initiation of pitting corrosion have been postulated and discussed but to date there is no consensus on the mechanism of breakdown. Since all current mechanisms require Cl − interactions for oxide film breakdown in Cl − containing environments, the question is what is the nature of the interaction of aggressive anions such as Cl − with the passive film, adsorption and/or absorption, leading to pitting? This communication focuses on the interaction of Cl − with the passive oxide film on pure aluminum by reviewing and summarizing the available experimental data concerning Cl − interactions. It should also be noted that the observations for Cl − interactions with Al reviewed and summarized herein might not be applicable to all metals and alloys. Technologically important metals and alloys such as aluminum (Al), stainless steels, and nickel-based alloys exhibit corrosion resistance in a wide range of environments due to the presence of protective, passive oxides.1-90 The passive oxides behave as kinetic barriers, which inhibit further oxidation of the underlying thermodynamically reactive metals. However, in environments that contain aggressive anions such as chloride, Cl − , the passive film becomes unstable and degrades locally causing film breakdown and localized corrosion, which in turn decreases the service life of the materials. The consequence of discrete oxide failure is localized corrosion, which occurs in the forms of crevice corrosion in occluded sites and metastable or stable pitting corrosion on open surfaces. It is generally agreed that localized corrosion occurs in two distinct steps: initiation and propagation.A number of theories describing the initiation of pitting corrosion have been postulated and discussed.

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Section: Discussionmentioning

confidence: 99%

Section: Experimental Evidence For Chloride Incorporation In the Oxidmentioning

confidence: 99%

Chloride Ion Interactions with Oxide-Covered Aluminum Leading to Pitting Corrosion: A Review

Natishan

O’Grady

2014

J. Electrochem. Soc.

238

122

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“…The formation and corrosion protection mechanism of the metal cation layer of Zn 2+ is detailed in Figure A and B. Several studies have reported that an Al 2 O 3 layer (5‐ to 10‐nm thickness) is formed on aluminum alloys and that the layer has OH − sites at the solution/Al 2 O 3 interface . Hard and soft acids and bases (HSAB) theory has reported that hard acids and hard bases form strong bonds .…”

Section: Resultsmentioning

confidence: 99%

“…Several studies have reported that an Al 2 O 3 layer (5-to 10-nm thickness) is formed on aluminum alloys 10,12 and that the layer has OH − sites at the solution/Al 2 O 3 interface. 13,14 Hard and soft acids and bases (HSAB) theory has reported that hard acids and hard bases form strong bonds. 15,16 Commonly, Zn 2+ is categorized as a hard acid and OH − as a hard base; from this, it may be proposed that Zn 2+ easily bonds with the OH − on the Al 2 O 3 layer on aluminum alloys ( Figure 6A).…”

Section: Formation and Corrosion Protection Mechanism Of Metal Catimentioning

confidence: 99%

Auger electron spectroscopic analysis of corrosion products formed on A3003 aluminum alloy in model fresh water with different Zn²⁺ concentration

Otani

Islam

Sakairi³

et al. 2019

Surface & Interface Analysis

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The corrosion morphology and composition of corrosion products of A3003 formed in model fresh water with different Zn2+ concentrations were investigated by immersion tests combined with surface observations and analysis using an Auger electron spectroscope (AES). The cross‐sectional AES observations showed that the thickness of the corrosion product layer formed on A3003 decreases with increases in the Zn2+ concentration of the model fresh water. A cross‐sectional AES point analysis suggested that the corrosion products formed on the A3003 in the Zn2+ containing model fresh water (Zn2+ > 0.1 mM) have a multilayered structure and that the inner of Zn‐rich layer would have high corrosion protective properties.

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“…X-ray Photoemission Spectroscopy (XPS) measurements supported by DFT calculations of core electron spectra have made a convincing case that this substitution, without electron transfer, takes place on oxide-passivated Al metal surfaces. [51][52][53][54] Computationally, fluorination of AlOH groups using HF gas has been predicted to be energetically favorable. [62][63][64] In this work, we report DFT energetics associated with Cl − →OH − on the α-Al 2 O 3 (0001) surface using parameters consistent with those we apply to examine Cl − insertion into V O inside the oxide film, so that a comparison of mechanisms can be made.…”

Section: Introductionmentioning

confidence: 99%

First Principles, Explicit Interface Studies of Oxygen Vacancy and Chloride in Alumina Films for Corrosion Applications

Leung

2021

J. Electrochem. Soc.

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Pitting corrosion is a much-studied and technologically relevant subject. However, the fundamental mechanisms responsible for the breakdown of the passivating oxide layer are still subjects of debate. Chloride anions are known to accelerate corrosion; relevant hypotheses include Cl insertion into positively charged oxygen vacancies in the oxide film, and Cl adsorption on passivating oxide surfaces, substituting for surface hydroxyl groups. In this work, we conduct large-scale first principles modeling of explicit metal/Al 2 O 3 interfaces to investigate the energetics and electronic structures associated with these hypotheses. The explicit interface models allow electron transfer that mimics electrochemical events, and the establishment of the relation between atomic structures at different interfaces and the electronic band alignment. For multiple model interfaces, we find that doubly charged oxygen vacancies, which are key ingredients of the point defect model (PDM) often used to analyze corrosion data, can only occur in the presence of a potential gradient that raises the voltage. Cl − insertion into oxide films can be energetically favorable in some oxygen vacancy sites, depending on the voltage. We also discuss the challenges associated with explicit DFT modeling of these complex interfaces.

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Structure of Chlorine K-Edge XANES Spectra During the Breakdown of Passive Oxide Films on Aluminum

Cited by 26 publications

References 25 publications

Chloride Ion Interactions with Oxide-Covered Aluminum Leading to Pitting Corrosion: A Review

Chloride Ion Interactions with Oxide-Covered Aluminum Leading to Pitting Corrosion: A Review

Auger electron spectroscopic analysis of corrosion products formed on A3003 aluminum alloy in model fresh water with different Zn²⁺ concentration

First Principles, Explicit Interface Studies of Oxygen Vacancy and Chloride in Alumina Films for Corrosion Applications

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Structure of Chlorine K-Edge XANES Spectra During the Breakdown of Passive Oxide Films on Aluminum

Cited by 26 publications

References 25 publications

Chloride Ion Interactions with Oxide-Covered Aluminum Leading to Pitting Corrosion: A Review

Chloride Ion Interactions with Oxide-Covered Aluminum Leading to Pitting Corrosion: A Review

Auger electron spectroscopic analysis of corrosion products formed on A3003 aluminum alloy in model fresh water with different Zn2+ concentration

First Principles, Explicit Interface Studies of Oxygen Vacancy and Chloride in Alumina Films for Corrosion Applications

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Auger electron spectroscopic analysis of corrosion products formed on A3003 aluminum alloy in model fresh water with different Zn²⁺ concentration