Corrosion in the passive state

Fig. 4 shows a simple phase diagram for a metal (1) covered with a passivating oxide layer (2) contacting the electrolyte (3) with the reactions at the interfaces and the transfer processes across the film. This model is oversimplified. Most passive layers have a multilayer structure, but usually at least one of these partial layers has barrier character for the transfer of cations and anions. Three main reactions have to be distinguished. The corrosion in the passive state involves the transfer of cations from the metal to the oxide, across the oxide and to the electrolyte (reaction 1). It is a matter of a detailed kinetic investigation as to which part of this sequence of reactions is the rate-determining step. The transfer of O2 or OH- from the electrolyte to the film corresponds to film growth or film dissolution if it occurs in the opposite direction (reaction 2). These anions will combine with cations to new oxide at the metal/oxide and the oxide/electrolyte interface. Finally, one has to discuss electron transfer across the layer which is involved especially when cathodic redox processes have to occur to compensate the anodic metal dissolution and film formation (reaction 3). In addition, one has to discuss the formation of complexes of cations at the surface of the passive layer, which may increase their transfer into the electrolyte and thus the corrosion current density (reaction 4). The scheme of Fig. 4 explains the interaction of the partial electrode processes that are linked to each other by the elec-... 

Concepts, Models, and Experimental Approaches Separation between film relaxation (growth or dissolution) and metal corrosion in the passive state is meaningless except at perfect steady state beeause both aspeets of metal oxidation are intimately interrelated by the charge and mass balanees at the metal-film-electrolyte interface. 

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). 

As described in Sec. 11.3, the spontaneous corrosion potential of a corroding metal is represented by the intersection of the anodic polarization curve of metal dissolution with the cathodic polarization curve of oxidant reduction (Figs. 11—5 and 11-6). Then, whether a metal electrode is in the active or in the passive state is determined by the intersection of the anodic and cathodic polarization curves. 

Almost all metallic materials in practical environments perform their service in the state of spontaneous passivation, in which hydrated oxygen moleciiles or hydrogen ions act as oxidants to passivate the surfaces. Stainless steel is a good and widely known example of corrosion resistant metals it is spontaneously passivated and remains in the passive state with a thin passive oxide film even in fairly corrosive environments. 

Fig. 4. Schematic diagram of passive metals with electrode reactions (1) Metal corrosion (2) film formation (3) redox reactions with electron transfer to or from metal substrate (4a,b) complex formation and enhanced dissolution in the passive state.

Frame 3 typifies the condition sought after when using materials in the passive state. In this example, the cathodic polarization curve intersects only in the passive region, resulting in a stable and low corrosion current. This type of system can tolerate moderate upset conditions without the onset of accelerated corrosion. 

When the corrosion potential of a metal is made by some means more positive than the passivation potential, the metal will passivate into almost no corrosion because of the formation of a passive oxide him on the metal surface. As shown in Figure 22.17, the passivation of a metal will occur, if the cathodic polarization curve for the redox electron transfer of oxidant reduction goes beyond the anodic polarization curve for the metal ion transfer in the active state of metal dissolution. As far as the anodic polarization curve of metal dissolution exceeds the cathodic polarization curve of oxidant reduction, however, the corrosion potential remains in the active potential range and the metal corrosion progresses in the active state. An unstable passive state will arise if the cathodic polarization curve crosses the anodic polarization curve at two points, one in the passive state and the other in the active sate. In this unstable state, a passivated metal, once its passivity is broken down, can never be repassivated again because of its active dissolution current greater than the cathodic current of oxidant reduction. 

It will be shown later that the values of icrit, Epp, and ip, which are the important parameters defining the shape of the active-passive type of polarization curve, are important in understanding the corrosion behavior of the alloy. In particular, low values of icrit enhance the ability to place the alloy in the passive state in many environments. For this reason, the maximum that occurs in the curve at B (Fig. 5.4) is frequently referred to as the active peak current density or, in general discussion, as the active peak. It is the limit of the active dissolution current density occurring along the A region of the polarization curve. 

The anodic polarization of a given alloy base metal such as iron or nickel is sensitive to alloying element additions and to heat treatments if the latter influences the homogeneity of solid solutions or the kinds and distribution of phases in the alloy. The effect of chromium in iron or nickel is to decrease both EpP and icrit and hence to enhance the ease of placing the alloy in the passive state. The addition of chromium to iron is the basis for a large number of alloys broadly called stainless steels, and chromium additions to nickel lead to a series of alloys with important corrosion-resistant properties. 

PASSIVE-ACTIVE CELL - A corrosion cell in which the anode is a metal in that active state and the cathode is the same metal In the passive state. 

Which will be more corrosion resistant in the passive state ... 

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