A first quantitative XPS study of the surface films formed, by exposure to water, on Mg and on the Mg–Al intermetallics: Al3Mg2 and Mg17Al12

Liu, Ming; Zanna, Sandrine; Ardelean, Hélène; Frateur, Isabelle; Schmutz, Patrik; Song, Guang‐Ling; Atrens, Andrej; Marcus, Philippe

doi:10.1016/j.corsci.2009.02.017

Cited by 261 publications

(113 citation statements)

References 55 publications

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“…3c), further ensuring the existence of MgO. 47 XRD measurement was further conducted to ensure the component of the deposit and the pattern is shown in Fig. 3d.…”

Section: Resultsmentioning

confidence: 99%

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Nuli

Wang

et al. 2016

J. Electrochem. Soc.

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The electrolytes containing halide-free inorganic magnesium salt Mg(BH 4 ) 2 dissolved in ether solvents have shown reversible Mg deposition-dissolution performance. Herein, we improved the anodic stability of the electrolytes on non-inert stainless-steel electrode by mixing PP 14 TFSI ionic liquid with tetraglyme (TG) and dimethoxyethane (DME) ether solvents. The effect of mixing ratios and salt concentrations on the electrochemical behavior of the electrolyte were investigated. High anodic stability, good ionic conductivity, excellent cycling efficiency, feasibility of the preparation and good compatibility toward Mo 6 S 8 and TiO 2 insertion cathode make the electrolytes promising for the potential application in rechargeable magnesium batteries. 3-5 The development of magnesium electrolytes is considered as the most important challenge for the commercial application of rechargeable magnesium batteries because electrolyte properties govern battery performance and determine the class of cathodes to be utilized. 6 The significant progress is the reports of 0.25 mol L −1 Mg(AlCl 2 BuEt) 2 /THF (Bu=butyl, Et=ethyl) electrolyte 7,8 and 0.4 mol L −1 (PhMgCl) 2 -AlCl 3 /THF electrolyte, 9,10 which have high anodic stability (2.5 V and 3.3 V vs. Mg RE on inert Pt electrode, respectively) and reversibility of Mg deposition-dissolution. Recently, a family of novel boron based electrolytes with high ionic conductivity, excellent Mg deposition reversibility as well as high anodic potential were proposed.11,12 On the other hand, phenolate-based 13 and alkoxide-based 14 electrolytes exhibit air insensitive character and excellent magnesium depositiondissolution performance. Meanwhile, inorganic magnesium salt solutions synthesized by the acid-base reaction of MgCl 2 and Lewis acidic compounds such as AlCl 3 show high coulombic efficiency, low overpotential for magnesium deposition-dissolution and good anodic stability. [15][16][17][18] However, these electrolytes may corrode non-inert current collectors at lower anodic potentials duo to the presence of halides in the cation and anion components of the electrolytes, although some of these electrolytes have shown impressive stability against electrochemical oxidation.19 Hence, it is still necessary to find electrolytes with high stabilities on non-inert current collectors for a practical rechargeable Mg battery system. Nelson et al. showed that decreasing the chloride content in Mg electrolytes by switching the Lewis acid from AlCl 3 to Al(OPh) 3 greatly improves the anodic stability up to 5 V on both Pt and stainless steel electrodes.20 Ha et al. proposed a new class of electrolytes based on magnesium (II) bis(trifluoromethane sulfonyl)imide (Mg[N-(SO 2 CF 3 ) 2 ] 2 , Mg(TFSI) 2 ) dissolved in glymebased solvents with unique characteristics such as highly reduced corrosive nature toward the current collector, low volatility, high solvating power, and the ability to form an appropriate solvation sheath structure for Mg deposition-dissolution. 21 Recently, a whole new promisi...

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“…3c), further ensuring the existence of MgO. 47 XRD measurement was further conducted to ensure the component of the deposit and the pattern is shown in Fig. 3d.…”

Section: Resultsmentioning

confidence: 99%

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Nuli

Wang

et al. 2016

J. Electrochem. Soc.

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“…This overview of stress corrosion cracking (SCC) of magnesium (Mg) alloys builds on our critical reviews of Mg corrosion [1][2][3][4] and Mg SCC [5] ; and recent research to understand Mg corrosion [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] and SCC. [5,[22][23][24][25][26][27][28][29][30][31][32] Our critical review of Mg SCC [5] found little published on SCC of cast Mg alloys, particularly modern alloys.…”

Section: Introductionmentioning

confidence: 99%

Stress Corrosion Cracking of Magnesium Alloys

2011

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An overview is provided of our current understanding of SCC of Mg alloys. TGSCC is caused by an interaction of H with the microstructure so a detailed study of H-trap interactions is needed in order to design alloys resistant to TGSCC. This understanding is urgently needed because prior research indicates that many Mg alloys have a threshold stress for stress corrosion cracking of the order of half the yield stress in common environments including high-purity water.SCC fracture surface for AZ91 showing fracture of a β-particle ahead of the min crack

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“…Films formed on Mg alloys under humid air or aqueous corrosion conditions are typically based on mixtures of MgO and Mg(OH) 2 . 4,[7][8][9][10][11][12] Although MgO can offer a degree of protection under ambient dry atmospheric corrosion conditions, it can be readily hydrated in the presence of water or water vapor to form Mg(OH) 2 , which offers limited stability and reduced protectiveness. 4 Further, considerations based on Pilling-Bedworth (P-B) ratio have also been invoked for explaining the inability of Mg to establish a fully protective oxide film.…”

mentioning

confidence: 99%

Transmission Electron Microscopy Study of Aqueous Film Formation and Evolution on Magnesium Alloys

Unocic

Elsentriecy

Brady

et al. 2014

J. Electrochem. Soc.

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The films formed on ultrahigh purity Mg, Elektron 717 (ZE10A), and AZ31B in water at room temperature were characterized by TEM, XPS, and SIMS. The films consisted primarily of MgO, with surface regions also containing Mg(OH) 2 and MgCO 3 . SIMS suggested H throughout the films and into the underlying metal. Segregation of Zn to the metal/film interface and Al in the film was observed for AZ31B. Similar Zn film segregation was also detected for Elektron 717, along with Nd at the alloy/film interface and nano-size Zn 2 Zr 3 precipitates throughout the film. Implications of these findings on film growth are discussed. Magnesium and its alloys are lightweight structural materials of great interest for reduced vehicle weight and improved fuel efficiency in the automotive industry due to their good strength, low density, amenability to casting, and ease of recycling.1-3 A major drawback, however, is the poor corrosion resistance of Mg under many conditions. 4 Magnesium is considered the most reactive structural material and is susceptible to multiple forms of corrosion; including general dissolution, galvanic coupling, localized corrosion, and stress corrosion cracking. 2,3,5,6 Surface treatments/coatings are needed for many applications which result in increased cost and can be a source of component durability issues. 1The inability of Mg alloys to establish a continuous and fully protective surface film under many exposure conditions is a key factor underlying their susceptibility to corrosive attack. Films formed on Mg alloys under humid air or aqueous corrosion conditions are typically based on mixtures of MgO and Mg(OH) 2 .4,7-12 Although MgO can offer a degree of protection under ambient dry atmospheric corrosion conditions, it can be readily hydrated in the presence of water or water vapor to form Mg(OH) 2 , which offers limited stability and reduced protectiveness. 4 Further, considerations based on Pilling-Bedworth (P-B) ratio have also been invoked for explaining the inability of Mg to establish a fully protective oxide film. 13 Magnesium has a P-B ratio of ∼0.8, which places surface MgO in tension, and can result in a porous, cracked, nonprotective oxide layer. (Typically a P-B ratio of 1-2 is considered a minimum, but not sufficient prerequisite for protective film formation). Corrosion can be further significantly accelerated when aggressive electrolyte species such as chloride are present. 5,14 Alloying has been shown to modify surface film performance; 15 however, a detailed mechanistic understanding of how and why is frequently lacking.Extensive studies based on electrochemical assessment and surface film chemistry depth profiling of Mg alloys have been pursued by techniques such as Auger electron spectroscopy (AES), secondary ion mass spectroscopy (SIMS), X-ray photoelectron spectroscopy (XPS), etc. [16][17][18][19][20][21][22][23] However, what is lacking is a detailed nano/micro structural level picture of the film nature and alloy/film interface regions, particularly with regards to segregation of...

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A first quantitative XPS study of the surface films formed, by exposure to water, on Mg and on the Mg–Al intermetallics: Al3Mg2 and Mg17Al12

Cited by 261 publications

References 55 publications

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Stress Corrosion Cracking of Magnesium Alloys

Transmission Electron Microscopy Study of Aqueous Film Formation and Evolution on Magnesium Alloys

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