Active-passive

In order to remove tlie unwanted electrical activity associated witli deep-level impurities or defects, one can eitlier physically displace tlie defect away from tlie active region of tlie device (gettering) or force it to react witli anotlier impurity to remove (or at least change) its energy eigenvalues and tlierefore its electrical activity passivation). 

FIG. 28-9 Typical electrochemical polarization curve for an active/passive alloy (with cathodic trace) showing active, passive, and transpassive regions and other important features. (NOTE Epp = primary passive potential, Ecaa- — freely corroding potential). 

FIG. 28-10 Six possible types of behavior for an active/passive alloy in a corrosive environment. 

Spontaneous Passivation The anodic nose of the first curve describes the primary passive potential Epp and critical anodic current density (the transition from active to passive corrosion), if the initial active/passive transition is 10 lA/cm or less, the alloy will spontaneously passivate in the presence of oxygen or any strong oxidizing agent. 

Stress corrosion can arise in plain carbon and low-alloy steels if critical conditions of temperature, concentration and potential in hot alkali solutions are present (see Section 2.3.3). The critical potential range for stress corrosion is shown in Fig. 2-18. This potential range corresponds to the active/passive transition. Theoretically, anodic protection as well as cathodic protection would be possible (see Section 2.4) however, in the active condition, noticeable negligible dissolution of the steel occurs due to the formation of FeO ions. Therefore, the anodic protection method was chosen for protecting a water electrolysis plant operating with caustic potash solution against stress corrosion [30]. The protection current was provided by the electrolytic cells of the plant. 

Check continuity zero and adjust Calibrate as required Chemical Cleaning Activation Passivation Rinse... 

Piping systems should be designed for an economic flow velocity. For relatively clean fluids, a recommended velocity range where minimum corrosion can be expected is 2 to 10 fps. If piping bores exist, maximum fluid velocities may have a mean velocity of 3 fps for a 3/8-in. bore to 10 fps for an 8-in.-diameter bore. Higher flow velocities are not uncommon in situations that require uniform, constant oxygen supply to form protective films on active/passive metals. 

Figure 4-421. Corrosion characteristics of an active passive metal as a function of solution oxidizing power (eiectrode potential). (From Ref. [183].)...

Fig. 1.39 Schematic anodic polarisation curve for a metal. Region AB describes active dissolution of the metal. BC is the active/passive transition, with passivation commencing at B. Passivation is complete only at potentials higher than C. The metal is passive over the range CD...

Fig. 1.41 Schematic anodic polarisation curves for a passivatable metal showing the effect of a passivating agent that has no specific cathodic action, but forms a sparingly soluble salt with the metal cation, a without the passivating agent, b with the passivating agent. The passive current density, the active/passive transition and the critical current density are all lowered in b. The effect of the cathodic reaction c, is to render the metal active in case a, and passive...

The ease with which stainless steels can passivate then increases with the level of chromium within the alloy and so materials with higher chromium content are more passive (i.e. conduct a lower passive current density) and passivate more readily (i.e. the critical current density is lower and the active/passive transition is lower in potential). They are also passive in more aggressive solutions the pitting potential is higher. 

Bxoised area of substrate metal. In the case of passive metals defects in the passive film result in an active-passive cell with intense localised attack on the active area... 

Note that Reference" draws attention to the possibility of an increase of anodic polarisation of the more negative member of a couple leading to a decrease in galvanic corrosion rate. There can also be a risk of increased corrosion of the more positive member of a couple. Both these features can arise as a result of active/passive transition effects on certain metals in certain environments. 

The effects of concentration, velocity and temperature are complex and it will become evident that these factors can frequently outweigh the thermodynamic and kinetic considerations detailed in Section 1.4. Thus it has been demonstrated in Chapter 1 that an increase in hydrogen ion concentration will raise the redox potential of the aqueous solution with a consequent increase in rate. On the other hand, an increase in the rate of the cathodic process may cause a decrease in rate when the metal shows an active/passive transition. However, in complex environmental situations these considerations do not always apply, particularly when the metals are subjected to certain conditions of high velocity and temperature. 

It is convenient to consider three stages of anode polarisation with regard to temperature effects, (a) under film-free conditions, (b) under film-forming conditions and (c) at the active-passive transition. 

Thus the rate of change of ip under activation control is much faster than / i, which is under diffusion control, and for the same condition of solution velocity the two rates could become equal at some common temperature, i.e. = ip, and there is no active-passive transition. For many of the systems given in the table this temperature is about 100°C. Above this temperature the measured activation energy is lower and diffusion control is established. 

Active-passive transition It has been shown that /p, the current required to maintain a passive film, increases with temperature at a much greater rate than the critical current for passivation as a result of an activation-controlled process. At some temperature /p will exceed /pri,. and no active-passive transition will be observed, and more important no protection by a passive film is possible because of the high rate of dissolution. At this stage the slow process becomes the diffusion of reactants and control of the rate is... 

The influence of temperature on the anodic behaviour of nickel has been studied, and in acidic and neutral solutions the active-passive transition is not observed at temperatures greater than about 100°C (Fig. 4.21). 

Electrochemical noise. Fluctuations in potential or current from baseline values during electrochemical measurements are particularly prominent during active/passive transitions. This so-called electrochemical noise is of particular value in monitoring localised corrosion, i.e. pitting, crevice and deposit corrosion and stress-corrosion cracking . 

Although the first industrial application of anodic protection was as recent as 1954, it is now widely used, particularly in the USA and USSR. This has been made possible by the recent development of equipment capable of the control of precise potentials at high current outputs. It has been applied to protect mild-steel vessels containing sulphuric acid as large as 49 m in diameter and 15 m high, and commercial equipment is available for use with tanks of capacities from 38 000 to 7 600000 litre . A properly designed anodic-protection system has been shown to be both effective and economically viable, but care must be taken to avoid power failure or the formation of local active-passive cells which lead to the breakdown of passivity and intense corrosion. 

The potentiostat is particularly useful in determining the behaviour of metals that show active-passive transition. Knowledge of the nature of passivity and the probable mechanisms involved has accumulated more rapidly since the introduction of the potentiostatic technique. Perhaps of more importance for the subject at hand are the practical implications of this method. We now have a tool which allows an operational definition of passivity and a means of determining the tendency of metals to become passive and resist corrosion under various conditions. 

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. 

Pressurised water nuclear reactors require metals that will have a high degree of corrosion resistance to pure water at around 300°C. Laboratory testing of materials for this application have included potentiostatic polarisation experiments designed to clarify the active-passive behaviour of alloys as well as to establish corrosion rates. Since pressure vessels are used for this work, it is necessary to provide sealed insulated leads through the autoclave head . 

Active Loop the region of an anodic polarisation curve of a metal comprising the active region and the active-passive transition. 

Active-passive Transition the range of potential between the active (freely corroding) state and the passive state. 

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