Corrosion of magnesium

Makar, G. L.; Krüger, J.

doi:10.1179/imr.1993.38.3.138

Cited by 670 publications

(277 citation statements)

References 39 publications

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“…Standard spectra for Brucite (Mg(OH) 2 , RRUFF ID: R040077) and Epsomite (MgSO 4 · 7H 2 0, RRUFF ID: R150060) are from the RRUFF database. 54 The peak at 1075 cm −1 is likely to be related to CO 3 2− species. Instrument artifacts were subtracted from each spectrum.…”

Section: Potentiostatic Polarization Ofmentioning

confidence: 99%

“…It should be noted that the film forming mechanism may also be described by: [3] f It should be further noted that Reaction 2 would not be discerned by extrapolation of cathodic data into the anodic range as the H 2 generated from Reaction 2 requires local Mg dissolution and is not the same source as from the Vomer or Heyrovsky HER mechanism on a net cathodic surface.…”

mentioning

confidence: 99%

“…2 However, the poor corrosion resistance and complex dissolution behavior of Mg has limited its wider use as an engineering material. [3][4][5] One aspect associated with Mg dissolution which has not to date been mechanistically elucidated in full, is the phenomenon known as the negative difference effect (NDE). 3 This effect is characterized by an increase in the rate of hydrogen evolution with increasing anodic overpotential relative to the open circuit -which provides a local cathodic reaction for a significant portion of the anodic reaction.…”

mentioning

confidence: 99%

“…[3][4][5] One aspect associated with Mg dissolution which has not to date been mechanistically elucidated in full, is the phenomenon known as the negative difference effect (NDE). 3 This effect is characterized by an increase in the rate of hydrogen evolution with increasing anodic overpotential relative to the open circuit -which provides a local cathodic reaction for a significant portion of the anodic reaction. 6 This phenomenon confounds the understanding of Mg dissolution mechanisms, establishment of a Tafel law and other reaction kinetic parameters, as well as other issues including accurate analysis of corrosion rates from electrochemical impedance spectroscopy (EIS).…”

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confidence: 99%

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The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl⁻versus Cl⁻Free Solutions

Cain

Gonzalez-Afanador

Birbilis

et al. 2017

J. Electrochem. Soc.

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The anodic dissolution and associated hydrogen evolution of high purity Mg (80 ppmw Fe) was studied as a function of potential in unbuffered 0.6 M NaCl (pH ≈ 8.5), 0.6 M NaCl saturated with Mg(OH) 2 (pH ≈ 10.25), 0.1 M MgCl 2 (pH ≈ 5.6), 0.1 M Na 2 SO 4 (pH ≈ 5.5), and a 0.1 M Tris(hydroxymethyl)aminomethane hydrochloride (TRIS, pH ≈ 7.25) buffer solution via simultaneous mass loss, hydrogen volume collection, potentiostatic and potentiodynamic polarization, and inductively coupled plasma-optical emission spectroscopy (ICP-OES). The negative difference effect (NDE) was substantial in the unbuffered Cl − containing environments where Mg(OH) 2 formed on the surface and weak in 0.1 M Na 2 SO 4 . In contrast, the 0.1 TRIS buffered solution exhibited a positive difference effect and the absence of thick corrosion films. Mg(OH) 2 films formed on samples in Cl − spalled off easily whilst the Mg(OH) 2 films formed in 0.1 M Na 2 SO 4 were more tenacious, which suggests that film stability plays significant role in the NDE. Research and development of magnesium (Mg) and its alloys has greatly increased in the last 15 years primarily due to the demand for lightweight vehicles in the automotive and aerospace industries, 1 in addition to the exploration of Mg as an anode material in primary and secondary batteries.2 However, the poor corrosion resistance and complex dissolution behavior of Mg has limited its wider use as an engineering material.3-5 One aspect associated with Mg dissolution which has not to date been mechanistically elucidated in full, is the phenomenon known as the negative difference effect (NDE).3 This effect is characterized by an increase in the rate of hydrogen evolution with increasing anodic overpotential relative to the open circuit -which provides a local cathodic reaction for a significant portion of the anodic reaction.6 This phenomenon confounds the understanding of Mg dissolution mechanisms, establishment of a Tafel law and other reaction kinetic parameters, as well as other issues including accurate analysis of corrosion rates from electrochemical impedance spectroscopy (EIS). [7][8][9] There are several theories purporting to explain the origins of the NDE among which include noble impurity element enrichment, 10,11 non-faradaic mass loss via metal spalling, 12,13 formation and dissolution of hydrides and partially protective films, [14][15][16][17] and univalent Mg based dissolution followed by further oxidation of Mg + →Mg 2+ in solution (leading to hydrogen evolution from the reduction of water away from the electrode in the electrolyte);18 however, no consensus has been reached on the physical origins of the NDE.The contemporary paradigm for the manifestation of the NDE centers on evidence for the enhanced cathodic activity of dissolving Mg anodes;19 whereby numerous works confined within a relatively recent timeframe have elucidated such a phenomenon. Evidence of enhanced cathodic activity has been reported by Williams and coworkers through use of the scanning vibrating electrode techniqu...

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Section: Potentiostatic Polarization Ofmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl⁻versus Cl⁻Free Solutions

Cain

Gonzalez-Afanador

Birbilis

et al. 2017

J. Electrochem. Soc.

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“…The high reactivity of Mg and its alloys is one factor that hinders their wider usage, and therefore unambiguous characterization of Mg dissolution and the accompanying hydrogen evolution remains topical. [1][2][3][4][5] During Mg dissolution, the anodic and cathodic reactions are expressed by the following equations:…”

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The pH Dependence of Magnesium Dissolution and Hydrogen Evolution during Anodic Polarization

Rossrucker

Samaniego

Grote

et al. 2015

J. Electrochem. Soc.

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The dissolution of magnesium (Mg) has been investigated with an electrochemical flow cell coupled to downstream analysis. The setup allows for polarization experiments and simultaneous determination of the amount of dissolved magnesium ions via inductively coupled plasma -mass spectroscopy (ICP-MS). Additionally, Mg dissolution was compared to hydrogen evolution measurements in the flow cell and also in standard beakers. Experiments were performed in unbuffered NaCl and in buffered solutions of various pH to determine the influence of the pH on surface film stability and Mg dissolution. In borate buffer (pH 10.5), Mg(OH) 2 was found to be more stable than in unbuffered electrolyte. In the flow cell, the negative difference effect (NDE) was absent for low anodic polarization currents in a neutral buffered solution, whilst high anodic polarization currents and unbuffered electrolytes favored its existence. In beaker experiments, strong NDE was observed in a pH 10.5 buffer, and also in pH 7 and 3 buffers, but only at higher applied currents where the buffering capacity was locally overwhelmed. These observations validate the importance of the pH in near surface regions with respect to the stability of Mg-surface films and subsequent NDE.

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Korrosionsschützendes Legieren von Magnesiumbasiswerkstoffen. Teil 1: Dynamische Alkalisierung der Grenzschicht - Tertiäre Legierungssysteme

Kaese

Niemeyer

Tai

et al. 1999

Materials and Corrosion

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Der breiteren Anwendung von Magnesiumlegierungen steht u. a. eine hohe Korrosionsanfälligkeit entgegen. Die bisherigen legierungstechnischen Ansätze führten, insbesondere bei Benetzung oder bei Kontaktkorrosion, nur zu einem unbefriedigenden Korrosionswiderstand. Es werden Mechanismen der Magnesiumkorrosion, wie z. B. die anomale Selbstauflösung, sowie Prinzipien des korrosionsschützenden Legierens diskutiert: Alkalisierung, Mischoxidbildung und Salzbildner. Die Effekte des korrosionsschützenden Legierens werden für Mg‐Li‐, Mg‐Al‐Zn‐, Mg‐Li‐Al‐, Mg‐Li‐Al‐Zn‐ und Mg‐Li‐Ca‐Systeme in synthetischem Meerwasser, CO2‐ begastem Leitungswasser und 0,01M H2SO4‐ Lösung dargestellt. Die Auswirkungen einer Variation des Li‐Gehalts wird in Freibewitterung untersucht.

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Corrosion of magnesium

Cited by 670 publications

References 39 publications

The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl⁻versus Cl⁻Free Solutions

The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl⁻versus Cl⁻Free Solutions

The pH Dependence of Magnesium Dissolution and Hydrogen Evolution during Anodic Polarization

Korrosionsschützendes Legieren von Magnesiumbasiswerkstoffen. Teil 1: Dynamische Alkalisierung der Grenzschicht - Tertiäre Legierungssysteme

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Corrosion of magnesium

Cited by 670 publications

References 39 publications

The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl−versus Cl−Free Solutions

The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl−versus Cl−Free Solutions

The pH Dependence of Magnesium Dissolution and Hydrogen Evolution during Anodic Polarization

Korrosionsschützendes Legieren von Magnesiumbasiswerkstoffen. Teil 1: Dynamische Alkalisierung der Grenzschicht - Tertiäre Legierungssysteme

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The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl⁻versus Cl⁻Free Solutions

The Role of Surface Films and Dissolution Products on the Negative Difference Effect for Magnesium: Comparison of Cl⁻versus Cl⁻Free Solutions