Corrosion breakdown potential

Increasing concentrations of bicarbonate tended to raise the breakdown potentials but also increased the corrosion potentials. This, in combination with a high chloride concentration, high bicarbonate concentrations may raise the corrosion potentials such that they border on passivation breakdown. The increase in hysteresis loop size on potentiodynamic cycles with increasing bicarbonate concentration shows a lowered resistance to pitting attack and crevice corrosion. 

Variations in pH promoted increases in corrosion potentials from acid pH levels to neutral pH thereafter, however, corrosion potentials were lowered in alkaline solutions to more active values. Decreasing pH caused a lowering of breakdown potentials in the presence of Cl and an increase in the current densities for passivation. 

In 3% sodium chloride solution at 60°C the austenitic irons again show superior characteristics to the ferritic. The breakdown potentials determined in this environment, which provide a relative measure of the resistance to attack in neutral chloride solutions, are generally more noble for the austenitic irons than for the ferritic (Table 3.47). This indicates that the austenitic irons should show better corrosion resistance in such environments. 

It is somewhat less corrosion resistant than tantalum, and like tantalum suffers from hydrogen embrittlement if it is made cathodic by a galvanic couple or an external e.m.f., or is exposed to hot hydrogen gas. The metal anodises in acid electrolytes to form an anodic oxide film which has a high dielectric constant, and a high anodic breakdown potential. This latter property coupled with good electrical conductivity has led to the use of niobium as a substrate for platinum-group metals in impressed-current cathodic-protection anodes. 

The critical breakdown potential, which is the positive potential limit of stability of the oxide film. At this potential and more positive potentials, the oxide film is unstable with respect to the action of anions, especially halide ions, in causing localised rupture and initiating pitting corrosion. 

All of these three properties of the oxide films on metals are influenced by the anion composition and pH of the solution. In addition the potential of the metal will depend on the presence of oxidising agents in the solution. Inhibition of corrosion by anions thus requires an appropriate combination of anions, pH and oxidising agent in the solution so that the oxide film on the metal is stable (the potential then lying between the Flade potential and the breakdown potential), and protective (the corrosion current through the oxide being low). 

Figure 25 Current versus time behavior for Type 302 stainless steel in 1,000 ppm NaCl at (a) a potential between its repassivation and breakdown potentials, and (b) at a potential below its repassivation potential. Note the existence of an incubation time before stable localized corrosion occurs in (a). The small, short-lived current spikes during the first 400 s are due to the formation and repassivation of metastable pits, which can also be observed in (b), although they are of a smaller magnitude.

Figure 26 Corrosion potential vs. time for Type 410 stainless steel in 0.5 M NaCl + 0.01 M H202. The breakdown potential is indicated by the dotted line. Once this potential is exceeded, the potential falls as stable, localized corrosion begins to propagate.

These tests focused on the determination of a materials resistance to localized (pitting) corrosion. To accomplish this goal, three types of electrochemical experiments were conducted (cyclic polarization, electrochemical scratch, and potenti-ostatic holds) to measure several key parameters associated with pitting corrosion. These parameters were the breakdown potential, EM, the repassivation potential, Etp, and the passive current density, tpass. 

The critical pitting potential cpr lies between the breakdown potential and the protection potential and can be determined by the scratch repassivation method. In the scratch repassivation method for localized corrosion, the alloy surface is scratched and exposed to a constant potential. The current change is monitored as a function of time and this will show the influence of potential on the induction time and the repassivation time. A careful choice of the level of potential between the breakdown potential and the critical pitting potential can give the critical pitting potential for a chosen material in given conditions.42 (Scully)14... 

Fig. 13. Plot of breakdown potential vs. temperature for Alloy 600 in buffered 0.1 M NaCl solution. Flow velocity =0 cm/s [33]. Reproduced from Corrosion J. 41, 197 (1985) by permission of the Editor.

The free corrosion potential, breakdown potential and corrosion rate of 316L stainless steel are chloride concentration dependent. As the chloride concentration increased, the free corrosion potential and the breakdown potential became less noble. The corrosion rate increased as the chloride concentration increased as expected. 

Reduction in the corrosion resistance of the 316L stainless steel is attributed to the destruction of the passive film in the presence of chloride. The roughest surface of 200 grit showed early passivity breakdown at the highest rate of corrosion and lower breakdown potential compared with the rest of the surfaces. 

In the presence of aggressive anions such as chloride ions in solution, the passive film on metals occasionally breaks down leading the underlying metal into a localized type of corrosion. In general, as shown in Figure 22.26, the chloride-breakdown of passivity occurs beyond a certain critical potential, called the film-breakdown potential, Eb. The film-breakdown is then followed either by... 

FIGURE 22.26 Schematic polarization curves for anodic metal dissolution, passivation, passivity breakdown, pitting corrosion, and transpassivation Eb = film-breakdown potential and Ep]l — pitting potential. 

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