Applications of scanning electrochemical microscopy (SECM) for local characterization of AZ31 surface during corrosion in a buffered media

Different modes of scanning electrochemical mapping (SECM) such as surface generation/tip collection (SG/TC), amperometry, AC-SECM and potentiometry were employed to characterize the active/passive domains, hydrogen gas (H2) evolution and local pH on a corroding surface of AZ31 in simulated biological fluid (SBF). It was found that the main domains of H2 evolution are associated with lower insulating properties of the surface as well as higher local pH. The near surface pH was found to be highly alkaline indicating that, even in a buffered solution such as SBF, the local pH on a corroding AZ31 surface can be significantly different to the bulk pH. © 2014 Elsevier Ltd.

Exploring the use of the tripeptide Gly–Gly–His as a selective recognition element for the fabrication of electrochemical copper sensors

The modification of electrodes with the tripeptide Gly–Gly–His for the detection of copper in water samples is described in detail. The tripeptide modified electrode was prepared by first self-assembling 3-mercaptopropionic acid (MPA) onto the gold electrode followed by covalent attachment of the tripeptide to the self-assembled monolayer using carbodiimide coupling. The electrodes were characterized using electrochemistry, a newly developed mass-spectrometry method and quantum mechanical calculations. The mass spectrometry confirmed the modification to proceed as expected with peptide bonds formed between the carboxylic acids of the MPA and the terminal amine of the peptide. Electrochemical measurements indicated that approximately half the MPA molecules in a SAM are modified with the peptide. The peptide modified electrodes exhibited high sensitivity to copper which is attributed to the stable 4N coordinate complex the peptide formed around the metal ion to give copper the preferred tetragonal coordination. The formation of a 4 coordinate complex was predicted using quantum mechanical calculation and confirmed using mass spectrometry. The adsorption of the copper to the peptide modified electrode was consistent with a Langmuir isotherm with a binding constant of (8.1 ± 0.4) 1010 M−1 at 25 °C.

Monitoring batch treatment inhibitor performance continuously using electrochemical noise analysis

Electrochemical noise analysis (ENA) was used to monitor continuously the formation and deterioration processes of a commercial batch treatment inhibitor film of the type used for protecting against CO₂ corrosion in oilfields; ENA was shown to be able to follow effectively the formation and deterioration processes of batch treatment inhibitor films. As an inhibitor film formed, the current noise amplitude decreased rapidly and the noise resistance R_n, which is deducible from the voltage and current noise records, was found to increase sharply. Conversely, as the inhibitor film deteriorated, the current noise amplitude increased rapidly and R_n decreased rapidly. In the corrosion inhibition system studied, the noise resistance was confirmed to be similar to the linear polarisation resistance. Based on the calculation of R_n on a continuous basis, a technique is proposed to study fast corrosion processes.

Factors affecting the determination of electrochemical noise resistance

The similarity between electrochemical noise resistance (Rn) and polarization resistance (Rp) has been confirmed in many laboratories, and a new method for corrosion rate determination has been developed based upon this similarity. However, this method remains controversial. Some researchers have reported experimental results that did not support a similarity between Rp and Rn. Other researchers have found that this similarity does not hold true for every system. To address this controversy, factors affecting the measurement and calculation of Rn were investigated. Several factors - including instrument noise, direct current (DC) trend, noise sampling rates, and noise sampling duration - can affect the accuracy of Rn determination signiftcantly and, in some cases, can cause disagreement between Rn and Rp. It was recommended that a system check be carried out to avoid the influence of these factors.

Continuous corrosion rate measurement by noise resistance calculation

A commonly employed method of corrosion rate measurement is to determine the electrochemical impedance of the corroding material. One technique for estimating the impedance is the noise impedance calculation. While it has been shown to yield useful results, there are a number of problems that require attention. This paper identifies some of those problems-specifically, those of detrending and resolution-and provides a solution that allows continuous, time-varying noise resistance and noise impedance calculations to be performed with known time, frequency, and magnitude resolutions. Applications to synthetic and experimental data are included as illustrations

Electrochemical and DFT studies of quinoline derivatives on corrosion inhibition of AA5052 aluminium alloy in NaCl solution

Two quinoline derivatives, 8-aminoquinoline (8-AQ) and 8-nitroquinoline (8-NQ), have been used as inhibitors to examine their corrosion protection effect on AA5052 aluminium alloy in 3% NaCl solution. The weight-loss and electrochemical measurement have indicated that 8-AQ and 8-NQ play as anodic inhibitor to retard the anodic electrochemical process. SEM/EDS analysis clearly shows that 8-AQ and 8-NQ form a protective film on the AA5052 alloy surface. Density functional theory (DFT) calculation confirmed the formation of strong hybridization between the p-orbital of reactive sites in the inhibitor molecules and the sp-orbital of the Al atom. 8-aminoquinoline and 8-nitroquinoline may be useful as effective corrosion inhibitors for aluminium alloys.