Mechanistic Model with Empirical Pitting Onset Approach for Detailed and Efficient Virtual Analysis of Atmospheric Bimetallic Corrosion.

A mechanistic model of atmospheric bimetallic corrosion with a simplified empirical approach to the onset of localized corrosion attacks is presented. The model was built for a typical bimetallic sample containing aluminum alloy 1050 and stainless steel 316L sheets. A strategy was developed that allowed the model to be calibrated against the measured galvanic current, geometrical corrosion attack properties, and corrosion products. The pitting-onset simplification sets all pits to be formed at a position near the nobler metal and treated all pits as being of the same shape and size. The position was based on the location of the highest pitting events and the pit attributes on an average of the deepest pits. For 5 h exposure at controlled RH (85%, 91%, and 97%) and salt load (86 µg NaCl/cm2), the model was shown to be promising: both for analysis of local bimetallic corrosion chemistry, such as pH and corrosion products, and for efficient assessment of pitting damage by computing a single largest pit depth. Parametric studies indicated that the pitting-onset approximation deviated the most at the beginning of exposure and when RH was below 91%.

The influence of buffer system and biological fluids on the degradation of magnesium.

The influence of frequently used buffer system 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) compared to CO2 /HCO3- on the corrosion of magnesium is investigated. Samples were immersed in simulated body fluid (m-SBF) while monitored by electrochemical impedance spectroscopy (EIS) for up to 30 days. In CO2 /HCO3- the initial corrosion rate was 0.11 mm yr-1 . An inner protective layer of magnesium oxide was formed within the first 30 min exposure and subsequently covered by an outer layer of apatite within 24 h. The corrosion mechanism thereafter is best described as passive pitting with a porosity of ∼10%. Using HEPES as buffer agent increased the corrosion rate to 3.37 mm yr-1 . Cross sectional microscopy show a porous outer corrosion layer allowing rapid diffusion of aggressive ions through the film. Here the EIS results are best described by an active pitting model with an inner layer 5 to 10 times less protective compared to the inner layer formed without HEPES. Further the suitability of human whole blood and plasma as in vitro models for Mg degradation was evaluated. Mg corrosion caused coagulation after 24 h in both biological fluids. The corrosion during the first 24 h is similar to the corrosion in m-SBF with HEPES. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1490-1502, 2017.

Influence of strain on the corrosion of magnesium alloys and zinc in physiological environments.

During implantation load-bearing devices experience stress that may influence its mechanical and corrosion profile and potentially lead to premature rupture. The susceptibility to stress corrosion cracking (SCC) of the Mg-Al alloy AZ61 and Zn was studied in simulated body fluid (m-SBF) and whole blood by slow strain rate (SSR) testing in combination with electrochemical impedance spectroscopy (EIS) and further ex situ analysis including scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy. AZ61 was found to be highly susceptible to SCC. EIS analysis show that although the majority of cracking occurred during the apparent plastic straining, cracking initiation occurs already in the elastic region at ∼50% of the ultimate tensile strength (UTS). Shifts in EIS phase angle and open circuit potential can be used to detect the onset of SCC. Zinc demonstrated a highly ductile behavior with limited susceptibility to SCC. No significant decrease in UTS was observed in m-SBF but a decrease in time to failure by ∼25% compared to reference samples indicates some effect on the mechanical properties during the ductile straining. The formation of micro cracks, ∼10µm deep, was indicated by the EIS analysis and later confirmed by ex situ SEM. The results of SSR analysis of zinc in whole blood showed a reduced effect compared to m-SBF and no cracks were detected. It appears that formation of an organic surface layer protects the corroding surface from cracking. These results highlight the importance of considering the effect of biological species on the degradation of implants in the clinical situation. STATEMENT OF SIGNIFICANCE: Strain may deteriorate the corrosion properties of metallic implants drastically. We study the influence of load on the corrosion properties of a magnesium alloy and zinc by a combination of electrochemical impedance spectroscopy (EIS) and slow strain rate analysis. This combination of techniques has previously not been used for studying degradation in physiological relevant electrolytes. EIS provide valuable information on the initial formation of cracks, detecting crack nucleation before feasible in slow strain rate analysis. This sensitivity of EIS shows the potential for electrochemical methods to be used for in situ monitoring crack formation of implants in more applied studies.

Degradation of zinc in saline solutions, plasma, and whole blood.

The initial degradation of zinc has been investigated through exposures to simulated and real body fluids of increasing complexity: phosphate buffered saline (PBS), Ringer's saline solution, human plasma, and whole blood. Real body fluids were used to close the electrolyte gap between simulated and in vivo environment. Polarization of zinc in whole blood show a passive response not present in other electrolytes. The analysis shows a decrease in corrosion rate with time for plasma and whole blood and an increase for PBS and Ringer's. During exposure to plasma and whole blood a bi-layered corrosion product with poor adherence was formed over a uniformly corroding surface. The corrosion products comprise a mixture of inorganic material and biomolecules. Samples degrading in PBS were prone to localized corrosion and formed thick porous corrosion products of primarily zinc phosphates while in Ringer's solution a gel like layer of zinc carbonate was formed over an interface with shallow pits. The use of whole blood or plasma as electrolytes for short term in vitro evaluation of potential biodegradable metals may provide an improved understanding of the behavior in vivo, while Ringer's solution is preferred over PBS for long term degradation studies of zinc. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1141-1151, 2016.