Novel corrosion experiments using the wire beam electrode. (I) Studying electrochemical noise signatures from localised corrosion processes

This series of papers presents four novel experiments that were designed to study localised corrosion phenomena using an electrochemically integrated multi-electrode array namely the wire beam electrode (WBE). This present paper reports a WBE based experimental method that has been employed, for the first time, to study electrochemical noise patterns (called noise signatures) from localised corrosion processes. The objective of this work is to demonstrate the applicability of the WBE for investigating the origin of spontaneous electrode potential/current fluctuations and their effects on electrochemical processes. The key strategy of this work is to apply the WBE in a novel experimental set-up to simultaneously measure electrode potential noise and WBE current distribution maps--an approach that allows the direct comparison and correlation of electrochemical noise and corrosion events. Preliminary experiments have been carried out using a classic pitting corrosion system: stainless steel in a solution containing FeCl₃. A large number of anodic sites were found to exist on WBE surface at the very beginning of its exposure to the corrosion environment. Correlation between characteristic patterns in electrode potential noise and corrosion behaviour has been observed. More specifically, the characteristic sharp peaks in potential noise data (called noise signature I) were found to correlate with the sudden disappearance of single unstable anode in WBE current distribution maps. The characteristic noise pattern of quick potential changes followed by partial or no recovery (called noise signature II) was found to correspond with the massive disappearance of minor anodes in WBE current distribution maps. This result suggests that, in the corrosion system under study, electrode noise activities were associated with the disappearance of minor anodic sites, which lead to the eventual disappearance of most anodic sites. Localised corrosion was the result of the accelerated anodic dissolution of a small number of remaining anodic sites. The characteristics features in electrochemical noise and in WBE maps were reproducible.     

Monitoring localised corrosion in inhibited solutions using wire beam electrode–noise signatures method

Abstract

The objective of this work is to determine the nature of localised corrosion in inhibited solutions by establishing possible relationships between characteristic features in electrochemical noise and corrosion processes using an electrochemically integrated multielectrode system, namely the wire beam electrode (WBE) in combination with noise signatures method. Experiments have been carried out to simultaneously measure electrode potential noise and WBE current distribution maps from stainless steel (SS316L) WBE exposed to inhibited solutions containing 6%FeCl₃ solution with inorganic inhibitors including 2 wt-% sodium chromate (Na₂CrO₄), cerium chloride (CeCl₃) and lanthanum chloride (LaCl₃). Characteristic electrochemical noise signatures were found to correlate with characteristic changes in WBE current distribution maps that show corrosion rates distributions and the degree of localised corrosion. A new concept namely localisation parameter (LP) has been proposed to identify the degree of inhibition. Na₂CrO₄ effectively inhibited the pitting corrosion process and the LP successively decreased through out the corrosion process. With the presence of CeCl₃ and LaCl₃, pits on stainless steel in 6%FeCl₃ solution were not repassivated and an increase in the LP was observed for both inhibitors. The results suggest that the WBE method could be used in combination with the noise signatures as a sensitive technique for monitoring inhibiting effect on localised corrosion.     

Novel corrosion experiments using the wire beam electrode: (II) Monitoring the effects of ions transportation on electrochemical corrosion processes

An electrochemically integrated multi-electrode system namely the wire beam electrode (WBE) has been applied for the first time to study the effects of the transportation of electrochemically active species on the process, rate and pattern of electrochemical corrosion. The objective of this work is to demonstrate the applicability of the WBE method for investigating ion transportation related corrosion processes. A series of experiments have been carried out using WBEs made from mild steel and stainless steel wires. The WBE working surfaces were exposed to simulated diffusion-controlled corrosion environments where there were diffusion induced ions concentration gradients (termed diffusion-corrosion environment). Corrosion potential and current distribution maps (CPCD maps) were measured from WBE surfaces in continuous bases. Typical patterns have been identified from CPCD maps and the characteristics of these patterns have been found to depend heavily upon the type of electrode material and the type of corrosive ion. For mild steel WBE surface exposed to a diffusion-corrosion environment containing NiSO₄ or FeCl₃, the characteristic pattern in CPCD maps was found to emulate NiSO₄ or FeCl₃ concentration gradients, suggesting an ion-concentration controlled corrosion behaviour. However, when the mild steel WBE surface was exposed to a diffusion-corrosion environment containing NaCl, the characteristic pattern was found to show higher cathodic currents along the WBE edges with the magnitude decreasing in a contour-like manner towards the centre of the WBE surface, suggesting an oxygen concentration-controlled corrosion behaviour. When a stainless steel (SS316L) WBE surface was exposed to a diffusion-corrosion environment containing NiSO₄ or NaCl, the corrosion pattern appeared to be mainly determined by the random distribution of weak sites in passive film. When the SS316L WBE was exposed to a diffusion-corrosion environment containing FeCl₃, the CPCD map revealed a characteristic pattern that shows localised damage to passive film. This work demonstrates that the recognition and analysis of characteristic maps from WBE measurements can be used as a means of studying diffusion, migration and other forms of mass transportation related electrochemical corrosion processes.     

Novel corrosion experiments using the wire beam electrode. (IV) Studying localised anodic dissolution of aluminium

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) has been applied in novel experiments to study the anodic dissolution behaviour of aluminium (AA1100), which was exposed to corrosive media with and without the presence of corrosion inhibitor potassium dichromate. The objective of this work is to demonstrate the applicability of the WBE for investigating corrosion processes under anodic polarisation. Anodic current measurements and mapping have been made, for the first time, with the WBE surface being anodically polarised. Pitting potential as well as anodic dissolution profile has been successfully determined by mapping anodic dissolution currents over the anodically polarised WBE surface. The pitting potential determined using the WBE method was found to correlate well with that determined using the conventional pitting scan method; and the anodic dissolution profile determined using the WBE method was found to correlate with maps obtained using the scanning reference electrode technique (SRET). Potassium dichromate was found to significantly affect the pitting potential, anodic dissolution profile and pitting initiation characteristics of aluminium. Two mechanisms of localised corrosion initiation have been identified. For WBE surface under free corrosion or low anodic polarisation conditions, the initiation of localised corrosion was found to be due to the disappearance of minor anodes, which lead to accelerated dissolution of a few major anodes. For WBE surface under large anodic polarisation, the initiation of localised corrosion was found to be due to the formation of active new anodic sites. This work suggests that the WBE method is useful for understanding the electrochemical behaviour of localised anodic processes, and their dependence on externally controllable variables.     

Understanding the effects of electrode inhomogeneity and electrochemical heterogeneity on pitting corrosion initiation on bare electrode surfaces

The effects of electrode inhomogeneity (EI) and electrochemical heterogeneity (EH) on pitting corrosion initiation have been analysed by revisiting research findings reported in the literature and experimental evidences obtained in our laboratories using the wire beam electrode (WBE) method. Two mechanisms of pitting corrosion initiation have been identified on bare metal surfaces exposed directly to electrolytes. For WBE surface under free corrosion or low anodic polarisation conditions the initiation of pitting corrosion was found to be due to the disappearance of minor anodes, leading to accelerated dissolution of a few remaining major anodes. The nucleation stage of pitting corrosion appeared to be controlled by EI, while the propagation stage appeared to be determined by EH. For WBE surface under large anodic polarisation the initiation of pitting corrosion was found to be due to the formation of active new anodic sites, which is in agreement with the conventional mechanism of pitting nucleation.     

Pitting and crevice corrosion behaviour of high alloy stainless steels in chloride‐fluoride solutions

The localised corrosion resistance (pitting and crevice corrosion) of two high alloy stainless steels, namely superduplex (SD) and superaustenitic (SA), has been studied in chloride‐fluoride solutions at pH values ranging from 2 to 6.5. The pitting potential (E_pit) and crevice potential (E_cre) have been calculated for these test media using electrochemical techniques (continuous current). The Critical Pitting Temperature (CPT) and Critical Crevice Temperature (CCT) are in both materials lower then the room temperature. In spite of this fact and due to the high repassivation rate, the resistance of these materials to localised corrosion is high in the tested media. At the highest tested concentration of aggressive anions and pH 6.5 both materials undergo a generalised attack.     

Crevice corrosion and pitting detection on 304 stainless steel using electrochemical noise

Random fluctuations in current and voltage under free corroding conditions have been measured on austenitic steel 304 in sodium chloride solutions with different aggressiveness. The evolution of these fluctuations in time and frequency domains is analysed and related to the corrosion process on the surface electrode. When the metal is passive, the noise becomes white meanwhile during localised attack changes in the current and voltage can be found. Electrochemical noise (EN) measurements also showed the ability of the technique to distinguish between different corrosion processes such as pitting or crevice corrosion.     

A new method of studying buried steel corrosion and its inhibition using the wire beam electrode

An electrochemically integrated multi-electrode system namely the wire beam electrode (WBE) has been applied for the first time to study corrosion of mild steel buried in sand, with and without the presence of corrosion inhibitor potassium dichromate (K₂Cr₂O₇). Measurements of galvanic current distribution maps have been carried out during the exposure of the WBE to dry, damp and chlorinated sand environments. Characteristic changes in galvanic current distribution maps have been observed during the initiation and propagation of localised corrosion. Specifically, during corrosion initiation in damped sand, new anodes were found to initiate and corrosion appeared to be in general form. When the WBE was later exposed to chlorinated sand, massive disappearance of anodic sites was found to occur, resulting in accelerated anodic dissolution of a small number of remaining anodic sites. Addition of corrosion inhibitor K₂Cr₂O₇ to the sand environment was found to significantly reduce galvanic current only after an initial increase in galvanic current. This result suggests that K₂Cr₂O₇ behaved as an anodic inhibitor.     

The crevice corrosion behaviour of stainless steel in sodium chloride solution

The crevice corrosion behaviour of 13Cr stainless steel in NaCl solution was investigated mainly by electrochemical noise measurements, considering the influences of the crevice opening dimension (a) and the area ratio of the electrode outside the crevice to the one inside the crevice (r). Results show that the increase of r value prolongs the incubation period of crevice corrosion, but crevice corrosion develops rapidly once the crevice corrosion occurs. The crevice corrosion develops preferentially at the crevice bottom and then spreads to the whole electrode surface. Proton could reduce on the uncorroded area and hydrogen bubbles form inside the crevice.     

Understanding electrodeposition of polyaniline coatings for corrosion prevention applications using the wire beam electrode method

Polyaniline (PANI) films have been successfully electrodeposited on aluminium AA1100 electrode surfaces in acidic electrolytes as anti-corrosion coatings. The wire beam electrode (WBE) has been applied for the first time as a novel tool to monitor the electrodeposition processes; and also to understand the anti-corrosion performance and mechanism of the PANI coatings. During PANI electrodeposition, the WBE was polarised anodically, and anodic polarisation currents were measured from various locations over the WBE surface to produce anodic polarisation current maps (APC maps). Preliminary experiments have revealed that if an AA1100 electrode was not pre-treated, APC maps would show a localised anodic current distribution, resulting in a nonuniform PANI deposit. If the AA1100 electrode was pre-treated by a cathodic polarisation process, APC maps would show a random anodic current distribution, leading to a PANI coating covering the whole electrode surface. When exposed to a corrosive environment, PANI coatings were found to prevent localised corrosion of AA1100, primarily by enhancing its passive film rather than by a barrier mechanism. However, a nonuniform PANI coating has been found to accelerate general corrosion of AA1100. These results suggest that the WBE is a practical tool for monitoring, characterising and optimising PANI electrodeposition processes and for evaluating the anti-corrosion performance of PANI coatings.     

A double‐mode cell to measure pitting and crevice corrosion

Pitting corrosion and crevice corrosion of passivated steels were measured by using a double‐mode syringe electrolyte cell built on an environment chamber. The setup, when set in noncontact mode, could measure pitting potentials and critical temperatures, and crevice corrosion potentials if in contact mode. It could be employed to distinguish the pitting and crevice corrosion damage of reinforcing steel in concrete.     

Loch- und Spaltkorrosion von Chrom- und Chromnickelstählen in chloridhaltigen Lösungen

Pitting and crevice corrosion of stainless steels in chloride solutions In practice stainless steels in chloride containing waters are found to be susceptible to crevice corrosion and pitting. Corrosion tests were carried out on AISI 304 L stainless using a simulated crevice and the compositions of the electrolyte in the crevice determined. Long term potentiostatic tests were used to determine the critical potentials for crevice corrosion (U_S), for various steels in sodium chloride solutions at different concentrations and temperatures. The steels studied were 22 CrMo V 121, X 22 CrNi 17 and AISI 304 L. Like the critical pitting potential (U_L), U_S was found to have a strong dependence on the chloride content of the external solution. At higher concentrations the two potentials were similar. At lower concentrations the U_S was lower than U_L. The knowledge of these critical potentials together with well known rest potentials for a steel in an electrolyte of known concentration, allows conclusions to be drawn about its susceptibility to pitting and crevice corrosion. The method is suitable also for other passive metals.     

Electrochemical evaluation of under-deposit corrosion and its inhibition using the wire beam electrode method

A new experimental method has been applied to evaluate under-deposit corrosion and its inhibition by means of an electrochemically integrated multi-electrode array, namely the wire beam electrode (WBE). Maps showing galvanic current and corrosion potential distributions were measured from a WBE surface that was partially covered by sand. Under-deposit corrosion did not occur during the exposure of the WBE to carbon dioxide saturated brine under ambient temperature. The introduction of corrosion inhibitor imidazoline and oxygen into the brine was found to significantly affect the patterns and rates of corrosion, leading to the initiation of under-deposit corrosion over the WBE.     

Heterogeneous corrosion of mild steel under SRB-biofilm characterised by electrochemical mapping technique

Heterogeneous corrosion of mild steel under sulphate reducing bacteria (SRB)-biofilm was characterised by wire beam electrode (WBE) technique and electrochemical impedance spectrum. The potential/current distributions of the WBE under SRB-biofilm showed that the potential maps could not indicate the localised corrosion of steels beneath biofilm due to the fact that all wire electrodes were short-circuited by the highly conductive sulphide precipitates embedded in SRB-biofilm. Instead, the galvanic current maps may give a good indication. The characteristic of super-capacitance (0.21 F/cm²) of SRB-biofilm was attributed to the huge specific surface area of conductive pore walls inside biofilm.     

An experimental comparison of three wire beam electrode based methods for determining corrosion rates and patterns

Laboratory experiments have been carried out to examine the advantages and limitations of three wire beam electrode (WBE) based techniques, including the noise resistance R_n-WBE method, the overpotential-galvanic current method, and the galvanic current method, in determining corrosion rates and patterns. These techniques have been applied simultaneously to several selected corrosion systems of different characteristics. It has been found that the R_n-WBE method has advantages over other WBE based methods when applying to WBE surfaces under uniform corrosion. However, the R_n-WBE method has been found to be unsuitable for low noise level corrosion systems. It has also been found that both R_n-WBE and overpotential-galvanic current methods are similarly applicable to WBE surfaces under nonuniform corrosion. However, the galvanic current method has been found to be suitable only for WBE surfaces under highly localised corrosion. Some related issues regarding R_n calculation such as trend removal and its effects on corrosion mapping have also been discussed.     

Novel corrosion experiments using the wire beam electrode: (III) Measuring electrochemical corrosion parameters from both the metallic and electrolytic phases

The wire beam electrode (WBE) and the scanning reference electrode technique (SRET) have been applied in a novel combination to measure, for the first time, electrochemical parameters simultaneously from both the metallic and electrolytic phases of a corroding metal surface. The objective of this work is to demonstrate the application of this combined WBE-SRET method in obtaining unique information on localised corrosion mechanism, by investigating typical corrosion processes occurring over a mild steel WBE surface exposed to the classic Evans solution. The WBE method was used to map current and potential distributions in the metallic phase, and the SRET was used to map current or potential distribution in the electrolytic phase. It has been found that the combined WBE-SRET method is able to gain useful information on macro-cell electrochemical corrosion processes that involve macro-scale separation of anodes and cathodes. In such macro-cell corrosion systems, maps measured using WBE and SRET were found to correlate with each other and both methods were able to detect the locations of anodic sites. However the movement of the scanning probe during SRET measurements was found to affect the SRET detection of cathodic sites. In micro-cell corrosion systems where the separation of anodic and cathodic sites were less distinct, SRET measurement was found to be insensitive in detecting anodic and cathodic sites, while the WBE method was still able to produce results that correlated well with observed corrosion behaviour. Results obtained from this work suggest that the WBE-SRET method is applicable for understanding the initiation, propagation and electrochemical behaviour of localised corrosion anodes and cathodes, and also their dependence on externally controllable variables, such as solution pH changes and the existence of surface coatings.     

Localised corrosion of cathodically protected pipeline steel under the effects of cyclic potential transients

Cathodic protection (CP) may lose its effectiveness for protecting buried steel pipeline from soil corrosion due to the effects of potential excursions caused by stray currents. In this work, dynamic localised corrosion processes of buried steel due to the effects of cyclic potential transients have been visualised using an electrochemically integrated multi-electrode array, often referred to as the wire beam electrode (WBE). The focus has been on the understanding of the effect of cathodic transients. The WBE maps suggest that the amplitude of cathodic transient, as well as the ratio of anodic cyclic to cathodic cyclic, can significantly affect the corrosion rates and patterns. In particular, if the cathodic transient leads to a very negative potential, e.g. ?1350?mV_vs.CSE, rapid corrosion would occur on buried steel surface. These results have implications for CP parameter selection for preventing stray current-affected buried steel pipelines.     

Organic molecules showing the characteristics of localised corrosion aggravation and inhibition

The behaviour of imidazoline and an acid functionalised resorcinarene as steel corrosion inhibitors in carbon dioxide (CO₂)-saturated brine solutions has been studied using an electrochemically integrated multi-electrode array namely the wire beam electrode (WBE). Both imidazoline and resorcinarene acid provided excellent inhibition to general CO₂ corrosion; however imidazoline was found to aggravate localised corrosion by creating a small number of major anodes that focused on a small area of the WBE surface, leading to highly concentrated anodic dissolution. The resorcinarene acid showed distinctively different behaviour by generating a large number of minor anodes randomly distributing over the WBE surface, leading to insignificant general anodic dissolution. These results indicate that resorcinarene acid provided effective localised corrosion inhibition by promoting a random distribution of insignificant anodic currents.     

Crevice corrosion of Q235 carbon steels in a solution of NaHCO3 and NaCl

The crevice corrosion of Q235 carbon steels in a solution of NaHCO₃ and NaCl was investigated mainly by electrochemical noise. Three stages of crevice corrosion were found and include an induction stage, a transformation stage and a stable development stage. Principal component analysis and hierarchical agglomerative cluster analysis were used to identify the crevice corrosion stages. The electrode area ratio of the outer to the inner part of the crevice (r) significantly influenced the occurrence and development of crevice corrosion. The induction stage time increased as r increased.