Passive state

The passive state of a metal can, under certain circumstances, be prone to localized instabilities. Most investigated is the case of localized dissolution events on oxide-passivated surfaces [51, 106, 107, 108, 109, 110, ill, 112, 113, 114, 115, 116, 117 and 118]. The essence of localized corrosion is that distinct anodic sites on the surface can be identified where the metal oxidation reaction (e.g. Fe —> Fe + 2e ) dominates, surrounded by a cathodic zone where the reduction reaction takes place (e.g. 2Fi + 2e —> Fi2). The result is the fonnation of an active pit in the metal, an example of which is illustrated in figure C2.8.6(a) and (b). 

In this test equipment in a passive state is tested first in any of the four positions noted above for an OBE test. When successful, it is tested for one SSE test. If these tests are successful, then the following tests may be conducted to complete seismic testing. 

One number - SSE test under passive state or energized conditions as desired and the behaviour and performance of the equipment assessed. 

Surface films are formed by corrosion on practically all commercial metals and consist of solid corrosion products (see area II in Fig. 2-2). It is essential for the protective action of these surface films that they be sufficiently thick and homogeneous to sustain the transport of the reaction products between metal and medium. With ferrous materials and many other metals, the surface films have a considerably higher conductivity for electrons than for ions. Thus the cathodic redox reaction according to Eq. (2-9) is considerably less restricted than it is by the transport of metal ions. The location of the cathodic partial reaction is not only the interface between the metal and the medium but also the interface between the film and medium, in which the reaction product OH is formed on the surface film and raises the pH. With most metals this reduces the solubility of the surface film (i.e., the passive state is stabilized). 

Steel in cement mortar is in the passive state represented by field II in Fig. 2-2. In this state reinforcing steel can act as a foreign cathodic object whose intensity depends on aeration (see Section 4.3). The passivity can be lost by introduction of sufficient chloride ions or by reaction of the mortar with COj-forming carbonates, resulting in a considerable lowering of the pH. The coordinates then lie in field I. The concentration of OH ions can be raised by strong cathodic polarization and the potential lowered, resulting in possible corrosion in field IV (see Section 2.4). 

The fundamentals of this method of protection are dealt with in Section 2.3 and illustrated in Fig. 2-15. Corrosion protection for the stable-passive state is unnecessary because the material is sufficiently corrosion resistant for free corrosion conditions. If activation occurs due to a temporary disturbance, the material immediately returns to the stable passive state. This does not apply to the metastable passive state. In this case anodic protection is necessary to impose the return to the passive state. Anodic protection is also effective in the unstable passive state of the material but it must be permanently switched on, in contrast to the metastable passive state. 

It is known that the common austenitic stainless steels have sufficient corrosion resistance in sulfuric acid of lower concentrations (<20%) and higher concentrations (>70%) below a critical temperature. If with higher concentrations of sulfuric acid (>90%) a temperature of 70°C is exceeded, depending on their composition, austenitic stainless steels can exhibit more or less pronounced corrosion phenomena in which the steels can fluctuate between the active and passive state [19]. 

Anodic Protection-a technique for reducing corrosion of a metal surface via passing sufficient anodic current to it to cause its electrode potential to enter into the passive state. 

As the system passes from the active to the passive state the initial interaction depends on the composition of the aqueous phaseAn initial chemisorbed state on Fe, Cr and Ni has been postulated in which the adsorbed oxygen is abstracted from the water molecules. This has features in common with the metal/gaseous oxygen interaction mentioned previously. With increase in anodic potential a distinct phase oxide or other film substance emerges at thicknesses of 1-4 nm. Increase in the anodic potential may lead to the sequence... 

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... 

Passivity of a metal lies in contrast to its activity, in which the metal corrodes freely under an anodic driving force. The passive state is well illustrated by reference to a classical polarisation curve prepared poten-tiostatically or potentiodynamically (Figure 1.39). As the potential is raised... 

Certainly a thermodynamically stable oxide layer is more likely to generate passivity. However, the existence of the metastable passive state implies that an oxide him may (and in many cases does) still form in solutions in which the oxides are very soluble. This occurs for example, on nickel, aluminium and stainless steel, although the passive corrosion rate in some systems can be quite high. What is required for passivity is the rapid formation of the oxide him and its slow dissolution, or at least the slow dissolution of metal ions through the him. The potential must, of course be high enough for oxide formation to be thermodynamically possible. With these criteria, it is easily understood that a low passive current density requires a low conductivity of ions (but not necessarily of electrons) within the oxide. 

Whilst temperature coefficients suggest modest potential differences, these calculations do not take into account the large potential changes that can occur when thermal effects allow transition from active to passive states. 

Potential-current density (E-i) curves, which have been determined for a number of the austenitic cast irons and also for the nickel-free ferritic irons, indicate that in general the austenitic cast irons show more favourable corrosion characteristics than the ferritic irons in both the active and passive states. 

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... 

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

Let us mention some examples, that is, the passivation potential at which a metal surface suddenly changes from an active to a passive state, and the activation potential at which a metal surface that is passivated resumes active dissolution. In these cases, a drastic change in the corrosion rate is observed before and after the characteristic value of electrode potential. We can see such phenomena in thermodynamic phase transitions, e.g., from solid to liquid, from ferromagnetism to paramagnetism, and vice versa.3 All these phenomena are characterized by certain values... 

Figure 2. Transition from passive state to pit-formation state.

In the polarization curve for anodic dissolution of iron in a phosphoric acid solution without CP ions, as shown in Fig. 3, we can see three different states of metal dissolution. The first is the active state at the potential region of the less noble metal where the metal dissolves actively, and the second is the passive state at the more noble region where metal dissolution barely proceeds. In the passive state, an extremely thin oxide film called a passive film is formed on the metal surface, so that metal dissolution is restricted. In the active state, on the contrary, the absence of the passive film leads to the dissolution from the bare metal surface. The difference of the dissolution current between the active and passive states is quite large for a system of an iron electrode in 1 mol m"3 sulfuric acid, the latter value is about 1/10,000 of the former value.6... 

In the third case, the transpassive state appears at a more noble potential than the passive state, where the dissolution current that was suppressed at the passive region again increases. The boundary potential... 

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