Electrochemical testing techniques

Nickel-base alloys respond well to most electrochemical test techniques and show active-passive behavior in many environments. Due to their rapid repassivation, however, the results obtained with potentiod3mamic techniques can sometimes be affected by scan rate and immersion time prior to starting the test [5,6], Electrochemical techniques are useful for investigating localized corrosion resistance, ASTM G 61, Test Method for Conducting Cyclic Potentio-dynamic Polarization Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys, and general corrosion resistance, ASTM G 59, Practice for Conducting Potentiodynamic Polarization Resistance Measurements of nickel alloys. Electrochemical impedance measurement techniques have not been extensively applied to nickel alloys. 

There are several ASTM standards that describe electrochemical testing techniques for the evaluation of corrosion behaviors of metal materials. Two useful methods are ASTM G5 - 94 Standard Reference Test Method for Making... 

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. 

A wide variety of steady and transient, in situ and ex situ, AC and DC methods have been developed to smdy electrochemical system behavior. To fully understand and apply these techniques requires a greater depth than the brief summary in this chapter can provide. For a more detailed explanation, the reader is referred to various texts devoted to electrochemical testing techniques, such as by Bard and Faulkner [1]. This chapter is designed to serve as an introduction to the potential techniques available to obtain a greater understanding and parameterization of the various polarization losses. 

Electrochemical Impedance Spectroscopy (EIS) and AC Impedance Many direct-current test techniques assess the overall corrosion process occurring at a metal surface, but treat the metal/ solution interface as if it were a pure resistor. Problems of accuracy and reproducibility frequently encountered in the application of direct-current methods have led to increasing use of electrochemical impedance spectroscopy (EIS). 

Use and Uimitations of Electrochemical Techniques A major caution must be noted as to the general, indiscriminate use of all electrochemical tests, especially the use of AC and EIS test techniques, for the study of corrosion systems. AC and EIS techniques are apphcable for the evaluation of very thin films or deposits that are uniform, constant, and stable—for example, thin-film protective coatings. Sometimes, researchers do not recognize the dynamic nature of some passive films, corrosion produc ts, or deposits from other sources nor do they even consider the possibility of a change in the surface conditions during the course of their experiment. As an example, it is note-... 

Warnings are noted in the literature to be careful in the interpretation of data from electrochemical techniques applied to systems in which complex and often poorly understood effects are derived from surfaces which contain active or viable organisms, and so forth. Rather, it is even more important to not use such test protocol unless the investigator fuhy understands both the corrosion mechanism and the test technique being considered—and their interrelationship. 

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. 

Electrochemical On-Line Corrosion Monitoring On-line corrosion monitoring is used to evaluate the status of equipment and piping in chemical process industries (CPI) plants. These monitoring methods are based on electrochemical techniques. To use on-line monitoring effectively, the engineer needs to understand the underlying electrochemical test methods to be employed. This section covers many of these test methods and their applications as well as a review of potential problems encountered with such test instruments and how to overcome or avoid these difficulties. 

Before electrochemical techniques are used in the evaluation of any situation involving microbes, tihe test protocol must receive considerable review by personnel quite experienced in both electrochemical testing and microbiologically influenced corrosion. It must be demonstrated that the method is capable of detecting and in some cases quantitatively measuring corrosion influenced by microbes. 

Electrochemical Characterization Technloues. Since corrosion Is an electrochemical process, It Is not surprising that a considerable amount of work has been reported over the years on electrical and electrochemical techniques for the study of the corrosion process. Leldhelser Ql.) and Szauer (12.> 11) have provided good reviews of the principal techniques. Walter has recently provided a review of DC electrochemical tests for painted metals (14). Both AC and DC methods have been employed to study a variety of Issues related to corrosion and corrosion protection. DC techniques are especially useful for studying substrate processes, while AC impedance techniques are most useful for studying processes relating to coated substrates and the performance of coatings. 

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. 

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