Electrochemical tests potentiostatic techniques

Standard test procedures are defined within ASTM standards ASTM G 59, Practice for Conducting Potentiodynamic Polarization Resistance Measurements G 5, "Standard Reference Test Method for Making Potentiostatic and Potentiodynamic Anodic Polarization Measurements G 106, Practice for Verification of Algorithm and Equipment for Electrochemical Impedance Measurements and G 102, Practice for Calculation of Corrosion Rates and Related Information from Electrochemical Measurements. Each of these methods describes a standard procedure or practice for the test method. A complete discussion of the technologies is beyond the scope of the current text. For the current text, the focus is on the application of the most simple and most widely used of these techniques, the polarization resistance measurement, ASTM G 59. The parameters discussed are, however, applicable concerns for all electrochemical tests. 

Electrochemical tests are rapid techniques to determine mechanisms, determine the effect of various parameters on corrosion rate, and screen out a large number of materials [43]. They usually involve measurement of corrosion potentials, corrosion currents, polarization curves, and electrochemical impedance. They are used to evaluate metals and alloys and the behavior of metallic, inorganic, and oiganic coatings. The simplest test involves the measurement of the corrosion potential and its use in conjunction with other measurements. A zero resistance ammeter (ZRA) is commonly used to measure corrosion currents between dissimilar metals and alloys. Controlled potentitd tests and anodic and cathodic polarization curves using potentiostats are the most commonly used electrochemical tests. These are powerful tools for investigating the effect of various parameters on corrosion behavior. These incorporate the use of cycUc polarization and polarization resistance for localized corrosion and corrosion rate measurements. Table 4 lists electrochemical tests that can be used for corrosion tests in the automobile industry. 

Electrochemical tests provide a means to understand the corrosion process, simulate service conditions, or accelerate evaluation of a material [27]. ASTM G 3, Practice for Conventions Applicable to Electrochemical Measurements in Corrosion Testing ASTM G 5, Standard Reference Test Method for Making Potentiostatic and Potentiodynamic Polarization Measurements and ASTM G 61, Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys provide background in some of these techniques. 

The potentiostatic electrolyas is, however, a useful preliminary research tool Fig. 2 illustrates a compartmented cell writable for testing on microscale, by steady state potentiostatic technique, the electrochemical features of a en system and the feasibility of macroscale coatings. (W), a metal rod of Fe or Zn, Cu, or A1 sealed... 

Potentiostatic and Potentiodynamic Anodic Polarization Measurements and ASTM G106 - 89 Standard Practice for Verification of Algorithm and Equipment for Electrochemical Impedance Measurements. Although most ASTM electrochemical testing techniques are developed for stainless steels, the test methods and procedures can be adapted for noble metals used in implantable medieal devices. 

In heterogeneous catalysis, the first tests on UPD were performed on bulk catalysts which allows, for the preparation of the bimetallic catalyst, easy control of the electrochemical potential by an external device (potentiostat). In the same way all electrochemical techniques, particularly the control of catalyst potential required for submonolayer deposition, can be extrapolated to metallic catalysts supported on conductive materials such as carbon or carbides [8]. 

Two other aspects of electrochemical phenomenology associated with localized corrosion should be appreciated before we discuss individual test techniques common observations during potentiostatic testing and common observations during open circuit testing. Careful interpretation of these tests can provide useful information on the processes that control localized corrosion. 

Most modem potentiostats provide at least four connections to the cell. These connections typically consist of a counter electrode (CE) that provides current to the ceU, a working electrode (WE) that provides measurement of the current through the cell, and at least two reference electrode inputs (RE) for voltage measurement. Potentiostats that have 4-terminal connections are capable of 2, 3 or 4-terminal testing of electrochemical cells (Figure 3.2.2). The 2-terminal test technique is used mainly for the measurement of high impedance materials where the impedance of cables is not significant (see Section 3.2.2.3). 

Several researchers experimented with electrochemically driven techniques. Budd and Booth used a potentiostatic approach [23]. Others have tried impressed current tests. Although both appeared promising, these procedures did not lend themselves to the multiple testing required for production control of heat treatment. Neither type of test has been standardized to date. 

Rates of corrosion can also be measured using an electrochemical technique known as potentiodynamic polarization. The potential of the test metal electrode relative to a reference electrode (commonly the saturated calomel electrode SCE) is varied at a controlled rate using a potentiostat. The resultant current density which flows in the cell via an auxiliary electrode, typically platinum, is recorded as a function of potential. The schematic curve in fig. 2 is typical of data obtained from such a test. These data can provide various parameters in addition to corrosion rate, all of which are suitable for describing corrosion resistance. The corrosion potential F corr is nominally the open circuit or rest potential of the metal in solution. At this potential, the anodic and cathodic processes occurring on the surface are in equilibrium. When the sample is polarized to potentials more positive than Scon the anodic processes, such as metal dissolution, dominate (Anodic Polarization Curve). With polarization to potentials more negative than Scorr the cathodic processes involved in the corrosion reaction such as oxygen reduction and hydrogen evolution dominate (Cathodic Polarization Curve). These separate halves of the total polarization curve may provide information about the rates of anodic and cathodic processes. The current density at any particular potential is a measure of the... 

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