Localized corrosion and inhibition studies using the wire beam electrode in conjunction with the electrochemical noise analysis and the scanning reference electrode techniques

Several new technical developments have been made based on the combined use of the wire beam electrode (WBE), electrochemical noise analysis (ENA) and the scanning reference electrode technique (SRET). These have included: (i) The WBE-R n method- the combined use of the WBE and the noise resistance (Rn) to map the rates and patterns of uniform or localized corrosion; (ii) The WBE-Noise Signatures method- the combined use of the WBE and the noise signature to detect the origination and propagation of localized corrosion; and (iii) The WBE-SRET method- the combined use of the WBE and SRET to investigate localized corrosion from both the metallic and electrolyte phases of a corroding metal surface. This paper presents a brief review on these novel methods and their applications for detecting general and localized corrosion, for mapping the rates of corrosion, and for studying corrosion inhibitors.

An electrochemical method for measuring localized corrosion under cathodic protection

 A new method has been developed to measure metal corrosion rates and their distribution under cathodic protection (CP). This method uses an electrochemically integrated multi-electrode array to take local measurements of cathodic current density while simulating a continuous metallic surface. The distribution of cathodic current densities obtained under CP was analyzed to estimate the anodic current component at each electrode of the array. Corrosion patterns determined by this new method have shown good correlation with visual inspection and surface profilometry of the multi-electrode array surface.

Electrochemical method for studying localized corrosion beneath disbonded coatings under cathodic protection

This paper presents a new method for measuring localized corrosion under disbonded coatings by means of an electrochemical sensor, denoted differential aeration sensor (DAS). It measures the distribution of electrochemical currents over an electrode array surface partially covered by a crevice that simulates a disbonded coating. The DAS has been evaluated using immersion tests at open circuit and under cathodic protection (CP) conditions. Under both conditions, anodic as well as cathodic current densities were detected within the crevice. A fundamental understanding for the detection of anodic currents under CP has been explained in terms of basic electrochemistry. Based on the current distribution data provided by the sensor, two different analysis methods have been used to estimate corrosion and its distribution. These methods consisted of a direct application of Faraday's Law to the anodic currents detected by the array, and on a sensor-specific method denoted corrected currents' method. It has been demonstrated that under diffusion controlled conditions this latter method produces a better corrosion estimation than the direct application of Faraday's Law. The corrected currents' method allowed the estimation of corrosion patterns outside the crevice under CP. Good correlation between electrochemical calculations and surface profilometry results has been obtained.

The restoration of the passivity of stainless steel Weldments in pickling solutions observed using electrochemical and surface analytical methods

In this study, a solution containing ammonium fluoride (NH4F) and nitric acid (HNO3) was used as an alternative to the conventional highly toxic pickling solution HF/HNO3 for pickling weldments of selected stainless steels including Type 316 stainless steel (UNS S31600), duplex stainless steel 2205 (UNS S32205), and super duplex stainless steel 2507 (UNS S32750). Electrochemical and surface analytical methods were used to understand the effects of pickling on the stainless steel weldments. Cyclic potentiodynamic polarization (CPP) test results indicated that the restoration of passivity of stainless steel weldments could be achieved by pickling the weldments in both HF/HNO3 solution and NH4F/HNO3 solutions. Scanning electron microscopy observation of the UNS S32750 weldment surface revealed that both the HF/HNO3 solution and the NH4F/HNO3 solution could remove the heat tint on the weldment. X-ray photoelectron spectroscopy analysis indicated that treatment in these two pickling solutions produced passive films with similar characteristics. Thus, this work suggests that the NH4F/HNO3 solution is a promising alternative to HF/HNO3 solution for the pickling of stainless steel weldments, and that the CPP test approach can be used in conjunction with surface analytical methods for further development of safer and environmentally friendly picklingsolutions.

Electrochemically monitoring localized corrosion patterns and CP effectiveness under disbonded coatings

© 2015 by Nace International. This paper presents new experimental evidences on the capability of a novel electrochemical corrosion monitoring sensor, which was recently conceived, for measuring localized corrosion under disbonded pipeline coatings. The sensor's design includes an artificial crevice for simulating the conditions developed under disbonded coatings and an electrode array for measuring current density distribution over its surface. The sensor capabilities were further evaluated by studying the dependency of corrosion patterns and current density distribution on the Cathodic Protection (CP) potential applied upon immersion in an aqueous environment. At the less negative CP potential, a good correlation was found between the inhomogeneous corrosion distribution under the disbonded coating as measured by the sensor and actual metal loss and corrosion attack observed on its surface at the end of the test. At more negative CP potentials no corrosion was detected or observed on the sensor's surface. In addition, characteristic changes in the cathodic current distribution at different CP potentials illustrated the possibility of employing the sensor to obtain valuable feedback on the performance of a given CP setup, without requiring its interruption or compensation of IR-drops. Furthermore, the sensor's capability to detect some of the effects of overprotection were shown at the most negative CP potential applied.

The effect of treatment time on the ionic liquid surface film formation: promising surface coating for Mg alloy AZ31

Mg alloys are attractive materials for medical devices. The main limitation is that they are prone to corrosion. A low toxicity surface coating that enables uniform, controlled corrosion at a desired rate (this usually means it must offer barrier functions for a limited time period) is desirable. Phosphate-based ionic liquids (ILs) are known to induce a coating that can reduce the corrosion rate of Mg alloys, Furthermore, some ILs are known to be biocompatible and therefore, controlling the corrosion behaviour of an Mg alloy and its surface biocompatibility can be achieved through adding an appropriate low toxic IL surface layer to the substrate. In this study, we have evaluated the cytotoxicity of three phosphate-based ILs to primary human coronary artery endothelial cells. Among them, tributyl(methyl)-phosphonium diphenylphosphate (P1,4,4,4dpp) shows the lowest cytotoxicity. Therefore, further work was aimed at developing an appropriate treatment method to produce a homogeneous and passive surface coating based on P1,4,4,4dpp IL, with the focus on investigating the effect of treatment time. The results showed that that the formation of IL coating on AZ31 has proceeded progressively, and treatment time plays an important role. An IL treatment at 100 °C with an extended treatment time of 5 h significantly enhanced corrosion resistance of the AZ31 alloy in simulated body fluid. Additionally, the corrosion morphology was uniform and there was no evidence of "localized pitting corrosion" observed. Such a performance makes this ionic liquid coating as a potential surface coating biodegradable Mg-based implants.