Passivity studies, potentiostat

Both the galvanostatic and potentiostatic method have their own particular spheres of application, and it is not always advantageous to reject the former in favour of the latter, although there is an increasing tendency to do so. Nevertheless, the potentiostatic method does have a distinct advantage in studies of passivity, since it is capable of defining more precisely the potential and current density at which the transition from the active (charge transfer controlled M to the passive state takes place this is fax... 

The determination of polarisation curves of metals by means of constant potential devices has contributed greatly to the knowledge of corrosion processes and passivity. In addition to the use of the potentiostat in studying a variety of mechanisms involved in corrosion and passivity, it has been applied to alloy development, since it is an important tool in the accelerated testing of corrosion resistance. Dissolution under controlled potentials can also be a precise method for metallographic etching or in studies of the selective corrosion of various phases. The technique can be used for establishing optimum conditions of anodic and cathodic protection. Two of the more recent papers have touched on limitations in its application and differences between potentiostatic tests and exposure to chemical solutions. ... 

The time factor in stepwise potentiostatic or potentiodynamic polarisation experiments is very important, because large differences can be caused by changes in the scanning rate. Since the steady state depends on the particular system and conditions of exposure, no set rule exists for the magnitude or frequency of potential changes. Chatfield etal. have studied the Ni/H2S04 system and have shown how becomes more passive with increase in sweep rate. 

The current-potential relationship ABCDE, as obtained potentiosta-tically, has allowed a study of the passive phenomena in greater detail and the operational definition of the passive state with greater preciseness. Bonhoeffer, Vetter and many others have made extensive potentiostatic studies of iron which indicate that the metal has a thin film, composed of one or more oxides of iron, on its surface when in the passive state . Similar studies have been made with stainless steel, nickel, chromium and other metals... 

Another contribution of the potentiostatic technique to s.c.c. studies has been the report that cracking prevails essentially at two potential levels for metals showing an active-passive transition. These potentials are located near the top and bottom of the passive region. Along the same lines, Uhlig and his co-workers have determined critical ranges of potential for s.c.c. , although their theoretical interpretation differs from that of the other references cited. 

The potentiostat has supplied an experimental tool for the study of anodic protection. The elucidation of passive behaviour made possible by poten-tiostatic anode polarisation curves allowed investigators to determine the conditions necessary for maintaining a metal in a stable passive condition by provision of a suitable environment, addition of cathodic alloying elementsand/or maintenance of the required potential by means of external anodic polarisation - . ... 

Cyclic potentiodynamic polarization method. Electrochemical studies of pitting corrosion usually indicate that pitting occurs only within or above a critical potential or potential range. Therefore the susceptibility of passive metals to pitting corrosion is often investigated by electrochemical methods such as potentiodynamic or potentiostatic... 

Noise analysis obtained from microelectrochemical investigations of stainless steels under potentiostatic conditions revealed that the current noise, expressed as standard deviation a of the passive current, increases linearly with the size of the exposed area, whereas the pitting potential decreases.47 However, to complete the electrochemical studies and distinguish between repassivating superficial pits and penetrating ones, microscopic studies are highly desirable. The scanning reference electrode technique (SRET) should be an appropriate complementary tool.28... 

Under -> open-circuit conditions a possible passivation depends seriously on the environment, i.e., the pH of the solution and the potential of the redox system which is present within the electrolyte and its kinetics. For electrochemical studies redox systems are replaced by a -> potentiostat. Thus one may study the passivating properties of the metal independently of the thermodynamic or kinetic properties of the redox system. However, if a metal is passivated in a solution at open-circuit conditions the cathodic current density of the redox system has to exceed the maximum anodic dissolution current density of the metal to shift the electrode potential into the passive range (Fig. 1 of the next entry (- passivation potential)). In the case of iron, concentrated nitric acid will passivate the metal surface whereas diluted nitric acid does not passivate. However, diluted nitric acid may sustain passivity if the metal has been passivated before by other means. Thus redox systems may induce or only maintain passivity depending on their electrode potential and the kinetics of their reduction. In consequence, it depends on the characteristics of metal disso-... 

In this study we applied these diagnostic criterion to evaluate whether the oxide films on tungsten are anion conducting in oxidizer solutions. As expected from the potentiodynamic polarization experiments, which show a constant current passivation regime, the steady state current density was found to be independent of potential in passive region using potentiostatic measurements. 

The electrochemistry of copper anodes in neutral and alkaline media has been studied in detail [223-226]. This complicated process includes, as a rule, the growth of ultrathin (several nanometers thick) films of CU2O, CuO, and also mixed and non-stoichiometric oxides. Until recently, it was assumed that cations do not affect the dissolution and passivation of copper. However, the first attempts to synthesize HTSCs and (or) their precursors showed that copper oxide films, formed when the potential of a copper electrode is cycled in a Ba(OH)2 solution, incorporate substantial amounts of barium [227]. This result was subsequently confirmed not only for potentiodynamic [228] but also for potentiostatic [229] oxidation modes. It has been suggested that Ba[Cu(OH)4] or Ba[Cu2(OH)6] forms in the supersaturated nearelectrode layer [229]. Similar studies with other alkaline-earth cations at high pH are difficult to conduct due to the poor solubility of the corresponding hydroxides. 

Whether the total corrosion process is determined by the kinetics of anodic metal dissolution or the cathodic process depends on the size of the cathode and the kinetics of the partial electrode processes. The slowest reaction is the rate-determining step, as is usual in kinetics. In the case of a well-passivated valve metal, this is most probably the cathodic reaction, whereas for metals with semiconducting oxides, the rate-determining step win he anodic metal dissolution. In order to study the partial reactions of pitting corrosion separately, potentiostatic experiments are preferred. The cathodic process is replaced hy the electronic circuit of the potentiostat to investigate the anodic metal... 

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