Accurate Electrochemical Measurement of Magnesium Corrosion Rates; a Combined Impedance, Mass-Loss and Hydrogen Collection Study

Abstract Experiments were conducted to enable the simultaneous measurement of electrochemical impedance and collection of hydrogen gas during the corrosion of pure magnesium in NaCl solutions. These results were then assessed along with the attendant specimen mass loss, providing three unique measures of magnesium corrosion for the same specimen. It was determined that analysis of impedance data, while accounting for a physically justified inductive response at low frequencies, enabled the determination of the polarization resistance, RP at the zero frequency limit. The determination of RP, as evaluated herein from electrochemical testing, provided excellent correlation to the mass loss and volume of hydrogen collected. This finding is elaborated in a broader discussion that critically addresses previous studies which have utilized the impedance behavior of magnesium and which claim electrochemical tests may underestimate Mg corrosion when attempting to use a charge transfer resistance at intermediate frequencies.

[1]  V. Barranco,et al.  Effect of the chemistry and structure of the native oxide surface film on the corrosion properties of commercial AZ31 and AZ61 alloys , 2011 .

[2]  M. Gibson,et al.  Corrosion behaviour of Mg-alloy AZ91E with atypical alloying additions , 2009 .

[3]  F. Mansfeld,et al.  Determination of corrosion rates by electrochemical DC and AC methods , 1981 .

[4]  G. Song,et al.  Corrosion mechanisms of magnesium alloys , 1999 .

[5]  D. Shoesmith,et al.  Tracking the corrosion of magnesium sand cast AM50 alloy in chloride environments , 2013 .

[6]  Giehyeon Lee,et al.  Reaction of zero-valent magnesium with water: Potential applications in environmental remediation , 2013 .

[7]  G. Tang,et al.  Electrochemical Behavior Al2O3 ∕ Al Coated Surgical AZ91 Magnesium Alloy in Simulated Body Fluids , 2008 .

[8]  J. Światowska,et al.  The anodic dissolution of Mg in NaCl and Na2SO4 electrolytes by atomic emission spectroelectrochemistry , 2010 .

[9]  D. Tallman,et al.  Use of Magnesium Alloys as Pigments in Magnesium-Rich Primers for Protecting Aluminum Alloys , 2009 .

[10]  J. McDermid,et al.  Technical Note: Examination of Focused Ion Beam-Sectioned Surface Films Formed on AM60B Mg Alloy in an Aqueous Saline Solution , 2012 .

[11]  D. C. Silverman Corrosion Rate Estimation from Pseudo-Inductive Electrochemical Impedance Response , 1989 .

[12]  M. Stern,et al.  Electrochemical Polarization I . A Theoretical Analysis of the Shape of Polarization Curves , 1957 .

[13]  Michel Keddam,et al.  Faradaic Impedances: Diffusion Impedance and Reaction Impedance , 1970 .

[14]  J. Scully,et al.  Sacrificial Anode-Based Galvanic and Barrier Corrosion Protection of 2024-T351 by a Mg-Rich Primer and Development of Test Methods for Remaining Life Assessment , 2011 .

[15]  A. Atrens,et al.  Corrosion behaviour of a nominally high purity Mg ingot produced by permanent mould direct chill casting , 2012 .

[16]  D. StJohn,et al.  The effect of zirconium grain refinement on the corrosion behaviour of magnesium-rare earth alloy MEZ , 2002 .

[17]  J. Kruger,et al.  Corrosion Studies of Rapidly Solidified Magnesium Alloys , 1990 .

[18]  C. Blanc,et al.  AC Impedance Spectroscopy in Characterizing Time-Dependent Corrosion of AZ91 and AM50 Magnesium Alloys Characterization with Respect to Their Microstructures , 2001 .

[19]  N Birbilis,et al.  Assessing the corrosion of biodegradable magnesium implants: a critical review of current methodologies and their limitations. , 2012, Acta biomaterialia.

[20]  G. Song,et al.  Self-corrosion, galvanic corrosion and inhibition of GW103 and AZ91D Mg alloys in ethylene glycol solution , 2013 .

[21]  Sachio Yamamoto,et al.  Solubility of hydrogen in water, sea water, and sodium chloride solutions , 1974 .

[22]  G. Song,et al.  Corrosion of ultra-high-purity Mg in 3.5% NaCl solution saturated with Mg(OH)2 , 2013 .

[23]  N. Birbilis,et al.  Evolution of hydrogen at dissolving magnesium surfaces , 2013 .

[24]  H. Takenouti,et al.  Use of impedance measurements for the determination of the instant rate of metal corrosion , 1972 .

[25]  M. Paunovic An Electrochemical Control System for Electroless Copper Bath , 1980 .

[26]  N. Pébère,et al.  The corrosion of pure magnesium in aerated and deaerated sodium sulphate solutions , 2001 .

[27]  N. Birbilis,et al.  Localized Corrosion of Binary Mg-Nd Alloys in Chloride-Containing Electrolyte Using a Scanning Vibrating Electrode Technique , 2012 .

[28]  Ricardo M. Souto,et al.  Spatially-resolved imaging of concentration distributions on corroding magnesium-based materials exposed to aqueous environments by SECM , 2013 .

[29]  J. Kruger,et al.  Corrosion of magnesium , 1993 .

[30]  N. Birbilis,et al.  Effect of pH on the Grain Size Dependence of Magnesium Corrosion , 2012 .

[31]  John R. Scully,et al.  Polarization Resistance Method for Determination of Instantaneous Corrosion Rates , 2000 .

[32]  J. Kish,et al.  Nature of Surface Film on Matrix Phase of Mg Alloy AZ80 Formed in Water , 2013 .

[33]  Florian Mansfeld,et al.  Electrochemical impedance spectroscopy (EIS) as a new tool for investigating methods of corrosion protection , 1990 .

[34]  J. Kish,et al.  Analysis of the surface film formed on Mg by exposure to water using a FIB cross-section and STEM–EDS , 2012 .

[35]  Mark E. Orazem,et al.  Measurement Models for Electrochemical Impedance Spectroscopy I . Demonstration of Applicability , 1992 .

[36]  Vincent Vivier,et al.  An Impedance Investigation of the Mechanism of Pure Magnesium Corrosion in Sodium Sulfate Solutions , 2007 .

[37]  J. N. Murray,et al.  Utilization of the Specific Pseudocapacitance for Determination of the Area of Corroding Steel Surfaces , 1988 .

[38]  Mark E. Orazem,et al.  Enhanced Graphical Representation of Electrochemical Impedance Data , 2006 .

[39]  E. Knystautas,et al.  Improving Corrosion Resistance of AZ91D Magnesium Alloy by Nitrogen Ion Implantation , 1996 .

[40]  S. Virtanen,et al.  Corrosion Behavior of Polypyrrole/AZ91D in Simulated Body Fluid Solutions and Its Functionalization with Albumin Monolayers , 2012 .

[41]  Geraint Williams,et al.  Localized Corrosion of Magnesium in Chloride-Containing Electrolyte Studied by a Scanning Vibrating Electrode Technique , 2008 .

[42]  N. Pébère,et al.  Investigation of magnesium corrosion in aerated sodium sulfate solution by electrochemical impedance spectroscopy , 1990 .

[43]  M. Gibson,et al.  Electrochemical behaviour and corrosion of Mg-Y alloys , 2011 .

[44]  A. Coy,et al.  Influence of microstructure and composition on the corrosion behaviour of Mg/Al alloys in chloride media , 2008 .

[45]  P. Volovitch,et al.  Aqueous Corrosion of Mg-Al Binary Alloys: Roles of Al and Mg , 2012 .

[46]  S. R. Taylor,et al.  Physical Interpretation of the Warburg Impedance , 1995 .

[47]  C. Blanc,et al.  Local Electrochemical Impedance Spectroscopy Applied to the Corrosion Behavior of an AZ91 Magnesium Alloy , 2003 .

[48]  Denny A. Jones Principles and prevention of corrosion , 1991 .

[49]  D. Tallman,et al.  Assessment of the corrosion protection of aluminium substrates by a Mg-rich primer: EIS, SVET and SECM study , 2008 .

[50]  G. Song,et al.  The anodic dissolution of magnesium in chloride and sulphate solutions , 1997 .

[51]  F. Mansfeld,et al.  Recording and Analysis of AC Impedance Data for Corrosion Studies , 1981 .

[52]  G. Bierwagen,et al.  Mg-rich coatings: A new paradigm for Cr-free corrosion protection of Al aerospace alloys , 2004 .