Contribution of Oxygen Reduction to Mg Corrosion: Experimental Evidence By Electrochemical Microprobes
Authors: Lamaka Sviatlana , Wang Cheng , Xu Wen , Zheludkevich Mikhail , Höche Daniel 
Published: February 2024

Unravelling the mechanisms of magnesium corrosion is vital for establishing reliable research methodologies, developing new alloys and predicting magnesium degradation behaviour. Hydrogen evolution reaction is widely regarded as by far the main cathodic process during corrosion of magnesium. Hence, tracing the amount of released hydrogen was thought to be a reliable measure of magnesium degradation rate. Recently, experimental evidences obtained by different methods have been presented by several groups that oxygen reduction (ORR) is important secondary cathodic reaction during Mg corrosion [1-8]. For model galvanic couple Al-Cu-Mg, oxygen consumption on the surface of Mg along with that on Cu was observed by using oxygen sensing microoptode [1]. A simultaneous measurement of local current density by scanning vibrating electrode technique (SVET) and local oxygen concentration by oxygen sensing microoptode found a strong oxygen consumption at the active corrosion sites on the surface of commercially pure Mg in NaCl electrolyte [2]. Then, the evidence for the varying contributions of ORR to the total cathodic process on Mg alloys during atmospheric and aqueous corrosion was presented based on newly developed respirometric methods [3-5]. While around 10% of the total cathodic current was ascribed to ORR during aqueous corrosion, up to 60% of the total corrosion process was shown to be due to the ORR contribution during simulated atmospheric corrosion with wet-dry cycles. Nanoparticle-based O2 imaging was used to map decreased O2 concentration at the interface of several Mg alloys exposed to simulated body fluids [6].
High ORR rate on a slowly corroding ultra-high-purity Mg (UHP-Mg) in NaCl electrolyte was shown in our recent work [7]. Comparing that with lower ORR rate for faster corroding commercial purity Mg (CP-Mg), the rate of ORR was found to depend on the growth rate of Mg(OH)2 , which is the main corrosion product of Mg in the simple saline solution. The formation of Mg(OH)2 impeded the diffusion of oxygen from bulk electrolyte to metal interface, preventing metallic Mg substrate from the interaction with oxygen. The distribution of local concentration of dissolved gaseous H2 and O2 assessed by amperometric Clark-type micorprobes at the interface of UHP-Mg and CP-Mg demonstrated the inverse relationship between HER and ORR, and supports the finding that diffusion-controlled ORR highly depends on the barrier property of corrosion products on the surface [8]. The contribution of ORR current to total cathodic current reached 29.1% for UHP-Mg, while only 0.9% for CP-Mg after 1 hour of immersion in NaCl solution. The contribution of ORR decreases with immersion time, due to the impeded access of dissolved O2 to Mg interface caused by thickening of Mg(OH)2 layer. A numerical model was developed considering the mixed potential diagram and measured local oxygen concentration.

REFERENCES:

[1] D. Snihirova, M. Taryba, S.V. Lamaka, M.F. Montemor, Corrosion inhibition synergies on a model Al-Cu-Mg sample studied by localized scanning electrochemical techniques, Corrosion Science, 112 (2016) 408-417.
[2] E.L. Silva, S.V. Lamaka, D. Mei, M.L. Zheludkevich, The Reduction of Dissolved Oxygen During Magnesium Corrosion, ChemistryOpen, 7 (2018) 664-668.
[3] M. Strebl, S. Virtanen, Real-Time Monitoring of Atmospheric Magnesium Alloy Corrosion, Journal of The Electrochemical Society, 166 (2019) C3001-C3009.
[4] M. Strebl, M. Bruns, S. Virtanen, Editors’ Choice—Respirometric in Situ Methods for Real-Time Monitoring of Corrosion Rates: Part I. Atmospheric Corrosion, Journal of The Electrochemical Society, 167 (2020) 021510.
[5] M. Strebl, M.P. Bruns, G. Schulze, S. Virtanen, Respirometric In Situ Methods for Real-Time Monitoring of Corrosion Rates: Part II. Immersion, Journal of the Electrochemical Society, (2021).
[6] B. Zeller-Plumhoff, A.R. Akkineni, H. Helmholz, D. Orlov, M. Mosshammer, M. Kühl, R. Willumeit-Römer, M. Gelinsky, Oxygen-sensitive nanoparticles reveal the spatiotemporal dynamics of oxygen reduction during magnesium implant biodegradation, NPJ Materials Degradation, 6 (2022) 95.
[7] C. Wang, D. Mei, G. Wiese, L.Q. Wang, M. Deng, S.V. Lamaka, M.L. Zheludkevich, High rate oxygen reduction reaction during corrosion of ultra-high-purity magnesium, NPJ Materials Degradation, 4 (2020) 42.
[8] C. Wang, W. Xu, D. Höche, M.L. Zheludkevich, S.V. Lamaka, Exploring the contribution of oxygen reduction reaction to Mg corrosion by modeling assisted local analysis, Journal of Magnesium and Alloys, 11 (2023) 100-109.

ACKNOWLEDGEMENTS: C. Wang, Wen Xu, thank China Scholarship Council for the funding, grants no. 201806310128 and 201908510177