Electrochemical potential noise

With the rapid developments of electrochemical techniques and the required instrumentation electrochemical impendance and electrochemical potential noise and current noise techniques are gaining prominence in corrosion studies. 

Electrochemical noise This is a non-perturbation method and is defined as random low frequency low amplitude fluctuations either of the potential or current in a corroding system. Analysis of the corrosion potential noise can provide information relating to both the mechanism and kinetics of the cor-... 

Simultaneous monitoring of the selfgenerated electrochemical potential and current noise using analogue and digital techniques has been evaluated as a tool for monitoring coating performance. These data obtained have been compared with those from a.c. in jedance techniques. 

Laboratory measurement procedures used for electrochemical data acquisition and analysis during the monitoring exercise are outlined, and particular emphasis is placed on the electrochemical noise techniques. Electrochemical current noise has been monitored between two identical electrodes and the potential noise between the working electrodes and a reference electrode. 

Electrochemical noise monitoring techniques have been used previously in studies of corrosion processes occurring on metals in a variety of environments. Initially, work was directed towards the monitoring of potential noise fluctua-... 

If we utilise the above equations to describe the low frequency noise signals observed with electrochemical systems, it is apparent that the potential noise signal will provide information pertaining to the value of the Stern Geary constant since ... 

The operation of molecular devices in wet systems can yield performances unobtainable in dry systems. For example, molecular devices in wet systems can provide characteristic electron transfer control. While wet systems have a disadvantage in performance speed because of the slow mobility of ions, they have a notable advantage in fine and precise control of the direction and kinetics of electron transfer, even at room temperature. This characteristic can lead to a low noise level, because electron transfer is governed by the absolute electrochemical potentials of a series of molecules coexisting in the system. 

One way to divide the types of electrochemical noise is by the manner in which it is collected. Potential noise refers to measurements of the open circuit potential of an electrode versus either a reference electrode or a nominally identical electrode. While measurements with a conventional reference electrode have the advantage of being relatable to thermodynamic conditions, these reference electrodes have their own noise associated with them that could complicate analysis. In addition, the application of noise monitoring to field conditions would be... 

Electrochemical noise consists of low-frequency, low-amplitude fluctuations of current and potential due to electrochemical activity associated with corrosion processes. ECN occurs primarily at frequencies less than 10 Hz. Current noise is associated with discrete dissolution events that occur on a metal surface, while potential noise is produced by the action of current noise on an interfacial impedance (140). To evaluate corrosion processes, potential noise, current noise, or both may be monitored. No external electrical signal need be applied to the electrode under study. As a result, ECN measurements are essentially passive, and the experimenter need only listen to the noise to gather information. 

Area normalization of ECN data is not as straightforward as with other type of electrochemical data (140). Current and potential noise may scale differently with electrode area. For example, if it is considered that the mean current is the sum of contributions from discrete events across the electrode surface, then the variance associated with the mean value will be proportional to the electrode area. The standard deviation of the current noise, o7, a measure of current amplitude, will then scale as the square root of the area. If is assumed that potential noise originates from current noise acting on the interfacial impedance, then aE will scale with the inverse root of the area. Therefore it is inappropriate to normalize current and potential noise by electrode area linearly. On the contrary, area normalization of noise resistance does appear to be appropriate. This is so because the potential and current noise have a constant relationship with one another. As a result, it is appropriate to report noise resistance in units of T> cm2, remembering that the total area for normalization is given by the sum of the areas on both working electrodes. 

The methods of measuring corrosion rates in the course of testing corrosion inhibitors are conventional weight loss, electrochemical techniques such as linear polarization resistance, potentiodynamic polarization, AC impedance, and electrochemical potential or current noise. 

Electrochemical noise measurements may be performed in the potentiostatic mode (current noise is measured), the galvanostatic mode (potential noise is measured), or in the ZRA mode (zero resistance ammeter mode, whereby both current and potential noise are measured under open-circuit conditions). In the ZRA mode, two nominally identical metal samples (electrodes) are used and the ZRA effectively shorts them together while permitting the current flow between them to be measured. At the same time, the potential of the coupled electrodes is measured versus a low-noise reference electrode (or in some cases a third identical electrode). The ZRA mode is commonly used for corrosion monitoring. 

More detailed information can be obtained from noise data analyzed in the frequency domain. Both -> Fourier transformation (FFT) and the Maximum Entropy Method (MEM) have been used to obtain the power spectral density (PSD) of the current and potential noise data [iv]. An advantage of the MEM is that it gives smooth curves, rather than the noisy spectra obtained with the Fourier transform. Taking the square root of the ratio of the PSD of the potential noise to that of the current noise generates the noise impedance spectrum, ZN(f), equivalent to the impedance spectrum obtained by conventional - electrochemical impedance spectroscopy (EIS) for the same frequency bandwidth. The noise impedance can be interpreted using methods common to EIS. A critical comparison of the FFT and MEM methods has been published [iv]. 

Figure 21.2 A schematic representation of an electrochemical cell under potentiostatic regulation, with sources of potential noise indicated as shaded circles and sources of current noise indicated as shaded double circles (see Gabrielli et al. ).

In another study [35], the electrochemical emission spectroscopy (electrochemical noise) was implemented at temperatures up to 390 °C. It is well known that the electrochemical systems demonstrate apparently random fluctuations in current and potential around their open-circuit values, and these current and potential noise signals contain valuable electrochemical kinetics information. The value of this technique lies in its simplicity and, therefore, it can be considered for high-temperature implementation. The approach requires no reference electrode but instead employs two identical electrodes of the metal or alloy under study. Also, in the same study electrochemical noise sensors have been shown in Ref. 35 to measure electrochemical kinetics and corrosion rates in subcritical and supercritical hydrothermal systems. Moreover, the instrument shown in Fig. 5 has been tested in flowing aqueous solutions at temperatures ranging from 150 to 390 °C and pressure of 25 M Pa. It turns out that the rate of the electrochemical reaction, in principle, can be estimated in hydrothermal systems by simultaneously measuring the coupled electrochemical noise potential and current. Although the electrochemical noise analysis has yet to be rendered quantitative, in the sense that a determination relationship between the experimentally measured noise and the rate of the electrochemical reaction has not been finally established, the results obtained thus far [35] demonstrate that this method is an effective tool for... 

If the passive film cannot be reestablished and active corrosion occurs, a potential drop is established in the occluded region equal to IR where R is the electrical resistance of the electrolyte and any salt film in the restricted region. The IR drop lowers the electrochemical potential at the metal interface in the pit relative to that of the passivated surface. Fluctuations in corrosion current and corrosion potential (electrochemical noise) prior to stable pit initiation indicates that critical local conditions determine whether a flaw in the film will propagate as a pit or repassivate. For stable pit propagation, conditions must be established at the local environment/metal interface that prevents passive film formation. That is, the potential at the metal interface must be forced lower than the passivating potential for the metal in the environment within the pit. Mechanisms of pit initiation and propagation based on these concepts are developed in more detail in the following section. 

Measurement of the electrochemical current noise is aimed at correlating the observed current fluctuations with breakdown and repair events that might lead to the formation of stable growing pits [53, 54], In view of this mechanistic interpretation, the application of statistical methods to the occurrence of current spikes and the observed probability of pit formation lead to a stochastic model for pit nucleation. The evaluation of current spikes in the time and frequency domain yields parameters such as the intensity of the stochastic process X and the repassivation rate r [53]. They depend on parameters such as the potential, state of the passive layer, and concentration of aggressive anions. 

Figure 15.9 Electrochemical current and potential noise forAISI 304L in 3.5 wt% NaCI solution at a transition Reynolds number of 2000. Reprinted from Ref [7]. Copyright (2007) with permission from Elsevier.

The other techniques of potentiodynamic scanning, EIS, harmonic impedance spectroscopy (HIS), and pure electrochemical current and potential noise are primarily laboratory methods that are used only in a limited way in field investigations. This is because of their relative expense, requirement for a low noise measurement environment, and clean and stable process conditions. However, simple qualitative electrochemical noise or pitting indications are used in a simple way in field applications to look at uniform versus nonuniform corrosion. Greater fluctuations and instability in the noise measurements are generally indicative of conditions leading to nonuniform or pitting corrosion. 

A relatively new application area for electrochemical techniques to corrosion studies that htis gained considerable interest over the last several years is the use of electrochemical current and potential noise measurements. Skerry was one... 

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