Active-passive alloys polarization curve

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. 3.3 Anodic polarization curve representative of active/passive alloys.

Fig. 5.35 Schematic polarization curve for an active-passive alloy having susceptibility to localized corrosion (pitting) due to chloride ions. Pitting initiates at Eb,pit- Small-dashed section is observed when chloride ion concentration initiates penetration of the passive film.

The result is a corrosion rate of about 10 mA/m2, icorr (L). In contrast, the alloy with the higher anodic peak would not be passivated. The polarization curves cross in the active potential range of the alloy resulting in an active corrosion rate corresponding to about 250 mA/m2. 

Mixed potential theory and the Levich equation are used to construct the anodic and cathodic polarization curve of the active-passive alloy and to estimate the value of the oxygen limiting diffusion current when a spontaneous passive film is formed on the surface. Figure 4.11 correlates the relationship between potential and current for the... 

E4.3. Construct an anodic polarization curve and calculate the critical passivation current density of an active-passive alloy using mixed potential theory with the following electrochemical parameters Econ = 0-b5V vs. SCE /corr= 10 " A/cm fca = 0.1, Epp= —0.3 V vs. SCE and /pass = 10 A/cm, Etr = + 0.9 V. 

Fig. 7.23 Polarization curve of active-passive alloy in the presence of chloride ions.

E7.8. Electrokinetic parameters of an active-passive alloy are given in Table E7.5 and the anodic polarization curve of the active-passive alloy in the presence of chloride ions is shown in Fig. 7.23. Pitting corrosion initiation occurs at 0.045 V vs. SHE. 

In the presence of oxidizing species (such as dissolved oxygen), some metals and alloys spontaneously passivate and thus exhibit no active region in the polarization curve, as shown in Fig. 6. The oxidizer adds an additional cathodic reaction to the Evans diagram and causes the intersection of the total anodic and total cathodic lines to occur in the passive region (i.e., Ecmi is above Ew). The polarization curve shows none of the characteristics of an active-passive transition. The open circuit dissolution rate under these conditions is the passive current density, which is often on the order of 0.1 j.A/cm2 or less. The increased costs involved in using CRAs can be justified by their low dissolution rate under such oxidizing conditions. A comparison of dissolution rates for a material with the same anodic Tafel slope, E0, and i0 demonstrates a reduction in corrosion rate... 

Most modern industrial materials are designed to be passive i.e., covered by an adherent, chemically inert, and pore-free oxide that is highly insoluble in aqueous solutions and hence dissolves at an extremely slow rate. Examples would be modern stainless steels, nickel-chromium-molybdenum, and titanium alloys. The concept of passivity is often defined by reference to the polarization curve for metals and alloys in aggressive acidic solutions, Fig. 22. This curve defines the potential regions within which the alloy would be expected to corrode actively or passively. 

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. 

Polarization curves for iron, chromium, and alloys with 1, 6, 10, and 14 weight percent (wt%) chromium in iron are shown in Fig. 5.24 the environment is 1 N H2SO4 at 25 °C (Ref 21). Iron and chromium are body-centered-cubic metals, and the alloys are solid solutions having this structure. The passivation potential (Epp), the active peak current density (icrit), and the passive state current density (ip) are decreased... 

Reference has been made to the observation that both anionic and cationic species in the environment can influence the anodic polarization of active-passive types of metals and alloys. Specific examples have related to the effect of pH as it influences the stability and potential range of formation of oxide and related corrosion product films. The effect of pH, however, cannot be treated, even with single chemical species, independent of the accompanying anions. For example, chloride, sulfate, phosphate, and nitrate ions accompanying acids based on these ionic species will influence both the kinetics and thermodynamics of metal dissolution in addition to the effect of pH. Major effects may result if the anion either enhances or prevents formation of protective corrosion product films, or if an anion, both thermodynamically and kinetically, is an effective oxidizing species (easily reduced), then large changes in the measured anodic polarization curve will be observed. 

Pitting corrosion is usually associated with active-passive-type alloys and occurs under conditions specific to each alloy and environment. This mode of localized attack is of major commercial significance since it can severely limit performance in circumstances where, otherwise, the corrosion rates are extremely low. Susceptible alloys include the stainless steels and related alloys, a wide series of alloys extending from iron-base to nickel-base, aluminum, and aluminum-base alloys, titanium alloys, and others of commercial importance but more limited in use. In all of these alloys, the polarization curves in most media show a rather sharp transition from active dissolution to a state of passivity characterized by low current density and, hence, low corrosion rate. As emphasized in Chapter 5, environments that maintain the corrosion potential in the passive potential range generally exhibit extremely low... 

Aluminum alloys are an exception. The oxide film formed in air or on immediate contact with an aqueous environment places aluminum in a passive state and an active-to-passive transition is not observed experimentally in the polarization curve. 

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