Corrosion Mechanisms and Electrochemical Interfaces: In Honor of Prof. Digby Macdonald

Special Issue Editors


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Guest Editor
1. National Center for Education and Research on Corrosion and Materials Performance, NCERCAMP-UA, The University of Akron, 302 E Buchtel Ave, Akron, OH 44325, USA
2. ROSEN USA, Inc., 14120 Interdrive East, Houston, TX 77032, USA
Interests: corrosion engineering; materials science; electrochemistry; chemistry of materials; metallurgy
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Special Issue Information

Dear Colleagues,

This Special Issue aims to gather scientific contributions that focus on corrosion mechanisms and electrochemical interface phenomena in material degradation processes.

An ample research scenario will be covered, including a range of corrosion and material degradation topics: localized corrosion, stress corrosion cracking, hydrogen embrittlement, crevice corrosion, atmospheric corrosion, corrosion inhibitors, microbiologically induced corrosion, as well as electrochemical kinetics and thermodynamics. In addition, advanced electrochemical techniques and computational studies for corrosion prevention and prediction, including stochastic and deterministic modeling approaches, as well as artificial intelligence and machine learning are also welcome. A comprehensive approach from theory to applications is considered for diverse topics such as energy systems, nuclear plants and repositories, geothermal, construction, transportation, aerospace, medical, environmental, materials sustainability, carbon capture, net zero emissions and circular economy aspects, among others.

In this regard, this Special Issue in Honor of Prof. Digby Macdonald is devoted to communications including experimental and theoretical studies on corrosion and electrochemical interfaces appealing to material degradation, protection and performance.

Dr. David M. Bastidas
Prof. Dr. Raman Singh
Guest Editors

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Published Papers (4 papers)

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Research

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26 pages, 4879 KiB  
Article
Mechanistic Analysis of Anodic Oxidation of Gold in KOH (0.1 M) Solution Using the Point Defect Model
by Zahed Ghelichkhah, Digby D. Macdonald and Gregory S. Ferguson
Corros. Mater. Degrad. 2024, 5(4), 450-475; https://doi.org/10.3390/cmd5040021 - 9 Oct 2024
Viewed by 945
Abstract
The potentiostatic, anodic formation of gold oxide at potentials of 0.55 to 0.80 V versus SHE in aqueous KOH (0.1 M) was studied using an impedance-based Point Defect Model (PDM). The film thickness and refractive indices at each formation potential were estimated using [...] Read more.
The potentiostatic, anodic formation of gold oxide at potentials of 0.55 to 0.80 V versus SHE in aqueous KOH (0.1 M) was studied using an impedance-based Point Defect Model (PDM). The film thickness and refractive indices at each formation potential were estimated using spectroscopic ellipsometry. The thickness of the oxide increases linearly with increasing applied voltage within this range. Mott-Schottky (MS) analysis showed that gold oxide formed in KOH (0.1 M) is an n-type semiconductor, and the dominant defect (Aui3+) density is calculated to be in the order of 1021–1022 (1/cm3). The steady-state current density of the oxide formation was independent of voltage, also in agreement with an n-type oxide. Reasonable agreement between PDM predictions and experimental observations of dominant defect density, steady-state current density, and thickness, demonstrates the value of the PDM in this system. Full article
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24 pages, 8467 KiB  
Article
Dissociative Adsorption of Hydrogen Molecules at Al2O3 Inclusions in Steels and Its Implications for Gaseous Hydrogen Embrittlement of Pipelines
by Yinghao Sun and Frank Cheng
Corros. Mater. Degrad. 2024, 5(2), 200-223; https://doi.org/10.3390/cmd5020008 - 2 Apr 2024
Cited by 1 | Viewed by 1672
Abstract
Hydrogen embrittlement (HE) of steel pipelines in high-pressure gaseous environments is a potential threat to the pipeline integrity. The occurrence of gaseous HE is subjected to associative adsorption of hydrogen molecules (H2) at specific “active sites”, such as grain boundaries and [...] Read more.
Hydrogen embrittlement (HE) of steel pipelines in high-pressure gaseous environments is a potential threat to the pipeline integrity. The occurrence of gaseous HE is subjected to associative adsorption of hydrogen molecules (H2) at specific “active sites”, such as grain boundaries and dislocations on the steel surface, to generate hydrogen atoms (H). Non-metallic inclusions are another type of metallurgical defect potentially serving as “active sites” to cause the dissociative adsorption of H2. Al2O3 is a common inclusion contained in pipeline steels. In this work, the dissociative adsorption of hydrogen at the α-Al2O3(0001)/α-Fe(111) interface on the Fe011¯ plane was studied by density functional theory calculations. The impact of gas components of O2 and CH4 on the dissociative adsorption of hydrogen was determined. The occurrence of dissociative adsorption of hydrogen at the Al2O3 inclusion/Fe interface is favored under conditions relevant to pipeline operation. Thermodynamic feasibility was observed for Fe and O atoms, but not for Al atoms. H atoms can form more stable adsorption configurations on the Fe side of the interface, while it is less likely for H atoms to adsorb on the Al2O3 side. There is a greater tendency for the occurrence of dissociative adsorption of O2 and CH4 than of H2, due to the more favorable energetics of the former. In particular, the dissociative adsorption of O2 is preferential over that of CH4. The Al-terminated interface exhibits a higher H binding energy compared to the O-terminated interface, indicating a preference for hydrogen accumulation at the Al-terminated interface. Full article
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17 pages, 3169 KiB  
Article
The AA7075–CS1018 Galvanic Couple under Evaporating Droplets
by Marvin Montoya, Juan Genesca and Rodrigo Montoya
Corros. Mater. Degrad. 2024, 5(1), 92-108; https://doi.org/10.3390/cmd5010005 - 7 Mar 2024
Cited by 2 | Viewed by 1853
Abstract
The galvanic corrosion behavior of the AA7075–CS1018 couple was examined in dynamic electrolytes using the ZRA technique. A modified electrochemical setup was developed to support the use of thin-film gel and liquid electrolytes on metallic surfaces. This allowed the collection of chemical information, [...] Read more.
The galvanic corrosion behavior of the AA7075–CS1018 couple was examined in dynamic electrolytes using the ZRA technique. A modified electrochemical setup was developed to support the use of thin-film gel and liquid electrolytes on metallic surfaces. This allowed the collection of chemical information, left behind by the liquid electrolyte during evaporation, through a thin-film gel. The analysis of the gel electrolyte film confirmed the acidification on AA7075 and the alkalinization on CS1018 but also offered novel insights on their dependence on the galvanic current. The galvanic current was proportional to the initial NaCl concentration in the range of 0.01 to 0.06 M. However, due to continuous evaporation, the NaCl concentration increased, limiting oxygen diffusion and decreasing the galvanic current, especially for electrolytes exceeding 0.06 M. The galvanic current was determined by considering the dynamic evolution (caused by the evaporation of the electrolyte film) of both the thickness of the electrolyte and its concentration. Full article
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Review

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15 pages, 5911 KiB  
Review
Distinctive Oxide Films Develop on the Surface of FeCrAl as the Environment Changes for Nuclear Fuel Cladding
by Haozheng Qu, Liang Yin, Michael Larsen and Raul B. Rebak
Corros. Mater. Degrad. 2024, 5(1), 109-123; https://doi.org/10.3390/cmd5010006 - 18 Mar 2024
Cited by 2 | Viewed by 1980
Abstract
The corrosion-resistant properties of IronChromium–Aluminum (FeCrAl) alloys have been known for nearly a century. Since the 1950s, they have been explored for application in the generation of nuclear power. In the last decade, the focus has been on the use of FeCrAl as [...] Read more.
The corrosion-resistant properties of IronChromium–Aluminum (FeCrAl) alloys have been known for nearly a century. Since the 1950s, they have been explored for application in the generation of nuclear power. In the last decade, the focus has been on the use of FeCrAl as cladding for uranium dioxide fuel in light water reactors (LWRs). The corrosion resistance of this alloy depends on the oxide that it can develop on the surface. In LWRs in the vicinity of 300 °C, the external surface oxide of the FeCrAl cladding could be rich in Fe under oxidizing conditions but rich in Cr under reducing conditions. If there is an accident and the cladding is exposed to superheated steam, the cladding will protect itself by developing an alpha aluminum film on the surface. Full article
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

1. Title: The importance of considering the service environment when studying and predicting the performance of corrodible structures

Author: Fraser King

Integrity Corrosion Consulting Ltd., Nanaimo, British Columbia, Canada V9T 1K2

Abstract

It should go without saying that when studying the corrosion behaviour of a component or structure the experimental conditions should reflect the service environment to which the object will be exposed. However, all too frequently, “accelerated” conditions involving applied potentials, elevated temperature, high solute concentrations, excessive strain or strain rates, etc. are used which complicates prediction of the in-service behavior or component lifetime. At best, it is necessary to extrapolate the results of these accelerated laboratory measurements to more realistic conditions, ideally based on a mechanistic understanding of the processes involved. At worst, accelerated laboratory tests may suggest corrosion processes that are not feasible or relevant to the service environment, potentially disqualifying a given material or design from consideration that would otherwise provide acceptable behaviour in service.

Examples of the need to properly take into account the service environment and the potential negative consequences of accelerated testing are given for the case of the corrosion behaviour of nuclear waste container materials.

2. Title: Validation of radiolysis models against experimental data in support of the prediction of the radiation-induced corrosion of copper nuclear used fuel containers

Authors: Scott Briggs,1 Mehran Behazin,1 and, Fraser King2*

1 Nuclear Waste Management Organization, Toronto, Ontario, Canada M4T 2S3

2 Integrity Corrosion Consulting Ltd., Nanaimo, British Columbia, Canada V9T 1K2

Abstract

Copper has been proposed as a container material for the disposal of used nuclear fuel in a number of countries worldwide. The container material will be subject to various corrosion processes in a deep geological repository, including radiation-induced corrosion (RIC) resulting from the g-irradiation of the near-field environment. A comprehensive model is being developed and implemented in COMSOL platform to predict the extent of RIC by coupling a radiolysis model to the interfacial electrochemical reactions on the container surface. An important component of the overall model is a radiolysis model to predict the time-dependent yield of oxidizing and reducing radiolysis products.

As a step in the model development, various radiolysis models have been validated against experimental data in order to select the most appropriate reaction scheme to then be coupled to the interfacial electrochemical processes. Experimental measurements of the yield of various radiolytic species are available for pure H2O and Clcontaining solutions, with and without a gas headspace. The results from these experiments have been compared with predictions from corresponding radiolysis models, including the effects of the partitioning of gaseous species (O2 and H2) at the gas-liquid interface. Different reaction schemes for the Cl radiolysis models are compared.




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