Heterogeneous electrode processes and localized corrosion

This book covers the areas of electrochemical heterogeneity and electrode inhomogeneity and their effects on nonuniform electrode processes, in particular, localized corrosion. It covers the fundamentals, experimental methods, and engineering aspects of electrochemical heterogeneity.

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.

Inhibiting localized corrosion of aluminum and aluminum alloy by rare earth metal compounds : behaviors and characteristics observed using an electrochemically integrated multi-electrode array

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) has been used to characterize the behavior of cerium chloride (CeCl3) and lanthanum chloride (LaCl3) in inhibiting localized corrosion of AA2024-T3 and AA1100. CeCl3 has been found to inhibit AA2024-T3 corrosion in 0.005 M sodium chloride (NaCl) solution by suppressing galvanic corrosion activities and by creating a large number of insignificant anodes. It has also been shown to inhibit localized corrosion of AA1100 in 0.5 M NaCl solution by promoting the random distribution of minor anodes. LaCl3 has been found to inhibit localized corrosion of AA2024-T3 at 1000 ppm, although its efficiency dropped significantly when its concentration decreased to 500 ppm. The addition of CeCl3 and LaCl3 to corrosion testing cells at later stages was unable to effectively suppress existing corrosion anodes.

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.

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 role of coarse intermetallics in the localized corrosion behaviour of AA 2024-T3 in low concentrated chloride media

Aluminium alloy (AA) 2024-T3 is an important engineering material due to its widespread use in the aerospace industry. However, it is very prone to localized corrosion attack in chloride containing media, which has been mainly associated to the presence of coarse intermetallics (IMs). In this work the corrosion behaviour of aluminium alloy 2024-T3 in low concentrated chloride media was investigated using microscopy and electrochemical methods. SEM observations have shown that intermetallics with the same nominal composition present heterogeneous reaction rates, and that both types of coarse IMs normally found in the AA 2024-T3 microstructure corrode. Moreover, EDS analyses have shown important compositional changes in the corroded IMs, evidencing the selective corrosion of their more active constituents and the onset of an intense oxygen peak, irrespective to the IM nature. TEM/EDS observations on non-corroded samples have evidenced the heterogeneous composition within the IMs. On the other hand, the results of the electrochemical investigations, in accordance with the SEM/EDS observations, have evidenced that IMs corrosion dominates the electrochemical response of the alloy during the first hours of immersion in the test electrolyte. © 2009 by NACE International.

Electrochemical methods for monitoring localized corrosion under cathodic protection

This research proposes two new electrochemical methods for measuring corrosion rates and their distribution under cathodic protection (CP). These methods were incorporated into a corrosion monitoring sensor that grow a great interest in the Australian energy pipeline industry.

Probabilistic modeling of structural deterioration of reinforced concrete beams under saline environment corrosion

For existing reinforced concrete structures exposed to saline or marine conditions, there is an increasing engineering interest in their remaining safety and serviceability. A significant factor is the corrosion of steel reinforcement. At present there is little field experience and other data available. This limits the possibility for developing purely empirical models for strength and performance deterioration for use in structural safety and serviceability assessment. An alternative approach using theoretical concepts and probabilistic modeling is proposed herein. It is based on the evidence that the rate of diffusion of chlorides is influenced by internal damage to the concrete surrounding the reinforcement. This may be due to localized stresses resulting from external loading or through concrete shrinkage. Usually, the net effect is that the time to initiation of active corrosion is shortened, leading to greater localized corrosion and earlier reduction of ultimate capacity and structural stiffness. The proposed procedure is applied to an example beam and compared to experimental observations,including estimates of uncertainty in the remaining ultimate moment capacity and beam stiffness. Reasonably good agreement between the results of the proposed procedure and the experiment was found