Electrochemical measurements corrosion testing

Although important contributions in the use of electrical measurements in testing have been made by numerous workers it is appropriate here to refer to the work of Stern and his co-workerswho have developed the important concept of linear polarisation, which led to a rapid electrochemical method for determining corrosion rates, both in the laboratory and in plant. Pourbaix and his co-workers on the basis of a purely thermodynamic approach to corrosion constructed potential-pH diagrams for the majority of metal-HjO systems, and by means of a combined thermodynamic and kinetic approach developed a method of predicting the conditions under which a metal will (a) corrode uniformly, (b) pit, (c) passivate or (d) remain immune. Laboratory tests for crevice corrosion and pitting, in which electrochemical measurements are used, are discussed later. 

A detailed and well-referenced account of electrochemical methods of testing has been written by Dean, France and Ketcham in a section of the book by Ailor. ASTM G5 1987 outlines standard methods for making potentiostatic and potentiodynamic anodic polarisation measurements and ASTM G3 1974 (R1981) gives conventions applicable to electrochemical measurements in corrosion testing. 

In view of the electrochemical nature of corrosion, it has seemed reasonable to many investigators to assume that suitable accelerated corrosion tests could be made by observing the response to electrolytic stimulation of the corrosion processes, or by attaching particular significance to the results of quickly made electrode potential and current measurements. 

Test method for sandwich corrosion test Recommended practice for preparing, cleaning, and evaluating corrosion test specimens Practice for aqueous corrosion testing of samples of zirconium and zirconium alloys Test method for corrosion testing of products of zirconium, hafnium and their alloys in water at 633 K or in steam at 673 K [metric] Recommended practice for conventions applicable to electrochemical measurements in corrosion testing... 

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. 

Environmental tests have been combined with conventional electrochemical measurements by Smallen et al. [131] and by Novotny and Staud [132], The first electrochemical tests on CoCr thin-film alloys were published by Wang et al. [133]. Kobayashi et al. [134] reported electrochemical data coupled with surface analysis of anodically oxidized amorphous CoX alloys, with X = Ta, Nb, Ti or Zr. Brusic et al. [125] presented potentiodynamic polarization curves obtained on electroless CoP and sputtered Co, CoNi, CoTi, and CoCr in distilled water. The results indicate that the thin-film alloys behave similarly to the bulk materials [133], The protective film is less than 5 nm thick [127] and rich in a passivating metal oxide, such as chromium oxide [133, 134], Such an oxide forms preferentially if the Cr content in the alloy is, depending on the author, above 10% [130], 14% [131], 16% [127], or 17% [133], It is thought to stabilize the non-passivating cobalt oxides [123], Once covered by stable oxide, the alloy surface shows much higher corrosion potential and lower corrosion rate than Co, i.e. it shows more noble behavior [125]. 

Absolute correlations between service performance and electrochemical measurements do not appear frequently in the literature. Based on 300 test systems. Bacon and coworkers (, correlated electrochemical resistance with exposure time. Recently, Mills ( also observed a correlation between salt fog corrosion and electrochemical resistance. We have found open circuit potential measurements to be extremely useful for the routine evaluation of high-nitrile polymer-based photocured coatings. 

ASTM G 3-89, Standard Practice for Conventions Applicable to Electrochemical Measurements in Corrosion Testing, American Society for Testing and Materials, Philadelphia, PA, USA, 1989, pp 56-64. 

This section provides a basic explanation of the underlying physical processes that control localized corrosion in order to lay the foundation for an understanding of the tests that are discussed in the next section. The manifestations of these physical processes through electrochemically measurable quantities are then discussed. Some generalized phenomenology is presented through illustrative examples from the literature. Full mechanistic understanding of localized corrosion has not yet been achieved. Information on the various models proposed can be found in review articles (11,12) and corrosion texts (13,14). 

Chapter 4 describes how the electrical nature of corrosion reactions allows the interface to be modeled as an electrical circuit, as well as how this electrical circuit can be used to obtain information on corrosion rates. Chapter 5 focuses on how to characterize flow and how to include its effects in the test procedure. Chapter 6 describes the origins of the observed distributions in space and time of the reaction rate. Chapter 7 describes the applications of electrochemical measurements to predictive corrosion models, emphasizing their use in the long-term prediction of corrosion behavior of metallic packages for high-level nuclear waste. Chapter 8 outlines the electrochemical methods that have been applied to develop and test the effectiveness of surface treatments for metals and alloys. The final chapter gives experimental procedures that can be used to illustrate the principles described. 

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. 

Apparatus for electrochemical measurements during corrosion fatigue. CF tests can be done using an apparatus designed by the Continental Oil Company, as shown in Figure 6.52.110,111 The polarization potential and current can be controlled for the four samples tests at the same time. The apparatus consists of a Monel tank in which four specimens are subjected to cyclic bending. The preliminary step in the experiment is to determine the displacement caused by the desired applied load. The exact stresses are then determined with the use of strain gages. 

Figure 5.25 Comparison of the results from stress corrosion tests with those from polarization curves at fast and slow potential sweep rates for different carbonate-bicarbonate solutions, indicating the extent to which the experimentally observed cracking range can be predicted from electrochemical measurements.8...

Electrochemical and Electrical Methods. Electrochemical and electrical methods for studying film properties and corrosion phenomena have been extensively reviewed (29-31). Comparisons of corrosion test results with direct current measurements of conductivity suggest that visible corrosion is associated with film resistance less than about 1 Mohm/cm, but this condition may well correspond with the occurrence of virtual pores in the film allowing development of local conductive pathways. In studies of the equivalent alternating current resistance as a function of frequency, Kendig and Leidheiser (44) found that the development of a region of slope -1 on a log permittivity versus log frequency plot... 

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