Impedance techniques types

Electrochemical tests This group includes the various electrochemical tests that have been proposed and used over the last fifty or so years. These tests include a number of techniques ranging from the measurement of potential-time curves, electrical resistance and capacitance to the more complex a.c. impedance methods. The various methods have been reviewed by Walter . As the complexity of the technique increases, i.e. in the above order, the data that are produced will provide more types of information for the metal-paint system. Thus, the impedance techniques can provide information on the water uptake, barrier action, damaged area and delamination of the coating as well as the corrosion rate and corroded area of the metal. However, it must be emphasised that the more comprehensive the technique the greater the difficulties that will arise in interpretation and in reproducibility. In fact, there is a school of thought that holds that d.c. methods are as reliable as a.c. methods. 

It can be seen that for severely degraded specimens, both the harmonic analysis and Impedance techniques are capable of detecting the presence of gross corrosion. The harmonics method provides a reasonable estimation of the corrosion rate when the Impedance data exhibits Warburg type behaviour. For less severely degraded specimens, especially those exhibiting blister attack, the Impedance method Is not as successful as the harmonic analysis technique. 

In the present work, steel surfaces polished, phosphated and painted are studied using AC Impedance technique In order to evaluate the protection efficiency of a commercial phosphatlng solution. The AC Impedance behavior of painted metal has been correlated with the Immersion time In the phosphatlng solution and with the desirability of a phospho-chromic rinse (18-23). A comparison of the Impedance behavior of two different types of commercial paints Is made for various durations of Immersion In sodium chloride solution at room temperature, and also for various temperatures at a given duration of Immersion. 

The fact of modulating the square root of Q was naturally supported by the results of the Levich theory in steady-state conditions [8]. With the increasing development of impedance techniques, aided by a sophisticated instrumentation [2], the authors of the present work promoted the use of impedance concept for this type of perturbation and introduced the so-called electrohydrodynamic (EHD) impedance [9, 10]. A parallel approach has been also investigated by use of velocity steps in both theoretical and experimental studies [5, 11, 12]. More recently, Schwartz et al. considered the case of hydrodynamic modulations of large amplitude for increasing the sensitivity of the current response and also for studying additional terms arisen with non linearities [13-15],... 

The proportionality constant between the applied potential and the charge due to the species ordering in the solution interfacial region is the double layer capacity. The study of the double layer capacity at different applied potentials can be done by various methods. One much used is the impedance technique, which is applicable to any type of electrode, solid or liquid, and is described in Chapter 11. Another method uses electrocapillary measurements. It was developed for the mercury electrode, being only applicable to liquid electrodes, and is based on measurement of surface tension. 

The a.c. impedance technique [33,34] is used to study the response of the specimen electrode to perturbations in potential. Electrochemical processes occur at finite rates and may thus be out of phase with the oscillating voltage. The frequency response of the electrode may then be represented by an equivalent electrical circuit consisting of capacitances, resistances, and inductors arranged in series and parallel. A simplified circuit is shown in Fig. 16 together with a Nyquist plot which expresses the impedance of the system as a vector quantity. The pattern of such plots indicates the type and magnitude of the components in the equivalent electrical network [35]. 

It was found subsequently that, although fractal geometry produces CPE behavior, in practice there is no relation between the CPE exponent and fractal dimensions [333, 334]. Qualitatively, however, higher fractal dimensions lead to smaller values of different type of fractals like Cantor bars [335-338] or Sierpihski carpets [339-341], for which different relations hold. This means that the impedance technique does not allow for the determination of the surface fractal dimension. Such information can be obtained by the analysis of current-time curves in the presence of diffusion to the surface [323, 324,342-344]. 

AC impedance technique is also effective to study the passive oxide. The passive oxide may have semiconductive property, so that the AC potential apphcation will induce the charge modulation in the oxide film. For example, when we consider n-type semi-condnctive oxide film rmder positive bias, i.e., nnder reverse bias condition, as shown in Fig. 8, a depression layer is formed in the oxide film. In the depression layer, space charge is extended. 

Ionization and condensation nuclei detectors alarm at the presence of invisible combustion products. Most industrial ionization smoke detectors are of the dual chamber type. One chamber is a sample chamber the other is a reference chamber. Combustion products enter an outer chamber of an ionization detector and disturb the balance between the ionization chambers and trigger a highly sensitive cold cathode tube that causes the alarm. The ionization of the air in the chambers is caused by a radioactive source. Smoke particles impede the ionization process and trigger the alarm. Condensation nuclei detectors operate on the cloud chamber principle, which allows invisible particles to be detected by optical techniques. They are most effective on Class A fires (ordinary combustibles) and Class C fires (electrical). 

However, as mentioned previously, gas-diffusion electrodes usually deviate substantially from traditional electrochemical—kinetic behavior, often being limited by multiple rate-determining factors and/or changes in those factors with overpotential or other conditions. In attempting to analyze this type of electrode, one of the most influential experimental techniques to take hold in the solid-state electrochemical literature in the last 35 years is electrochemical impedance spectroscopy (EIS)—also know as a.c. impedance. As illustrated in Figure 6, by measuring the sinusoidal i— response as a function... 

As the impedance and harmonic analysis techniques gave different types of data from each other, a direct comparison between Tables 1 and 2 is difficult. However, it should be anoted that G4 gave both semicircular behaviour and a reasonably high corrosion rate. This similarity is also true for A14 and A15. All and A13 showed smaller but still measurable corrosion rates, together with semicircular impedance behaviour and the absolute values measured varied similarly as before. 

Circuitry similar to that presented in Figure 8.13b has been used to analyze cells with impedances ranging from 102 to 1011 Q with 1% accuracy and resolution better than 1 part in 104 over a frequency range of 0.005 Hz to 10 kHz [14]. The technique has been especially useful for studies of the reaction kinetics of moderately fast chemical reactions. Kadish et al. [15] used phase-selective techniques to make ac impedance measurements to evaluate reference electrodes for use in nonaqueous solvents. Recent decreases in the cost of integrated function modules such as analog multipliers, oscillators, and phase-locked loops make this type of phase-selective instrumentation more accessible than ever. 

The second part of the book discusses ways in which information concerning electrode processes can be obtained experimentally, and the analysis of these results. Chapter 7 presents some of the important requirements in setting up electrochemical experiments. In Chapters 8—11, the theory and practice of different types of technique are presented hydrodynamic electrodes, using forced convection to increase mass transport and increase reproducibility linear sweep, step and pulse, and impedance methods respectively. Finally in Chapter 12, we give an idea of the vast range of surface analysis techniques that can be employed to aid in investigating electrode processes, some of which can be used in situ, together with photochemical effects on electrode reactions— photoelectrochemistry. 

A disadvantage of this type of technique is that the impedance of the whole cell is measured, whereas in the investigation of electrode processes one is interested in the properties of one of the electrodes. It is possible to reduce the contribution of the unwanted components by using an auxiliary electrode with an area large relative to that of the electrode being studied, and extrapolating the cell impedance to infinite frequency in order to remove contributions such as cell resistance. 

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