Nickel polarization curve

Fig. 11-10. Anodic polarization curves observed for metallic iron, nickel, and chromium electrodes in a sulfuric acid solution (0.5 M H 2SO 4) at 25°C solid curve = anodic metal dissolution current dot-dash curve s anodic oxygen evolution current [Sato-Okamoto, 1981.]...

Fig. 11-13. Anodic polarization curve of a metallic nickel electrode in a sulfuric add solution transpassivation arises at a potential relatively dose to the flat band potential because of p-type nature of the passive oxide film. [From Sato, 1982.]...

Fig. 11-16. Corrosion rate of metallic nickel in sulfate solutions (0.5 M NsjSO ) as a function of pH at 25 C inserted sub-figures are polarization curves of nickel electrodes in acidic solution and in basic solution. [From CScamoto-Sato, 1959.]...

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. 

Figure 2. (a) Kinetic curves and (b) polarization curves for nickel depc ition (1) for deposition of composites Ni-TiOz (2), Ni-tojOs (3), Ni-SnCh (4), Ni-FejOj (5), Ni-VjOs (6), Ni-MoCbA zOs (7). 

FIGURE 22.18 The corrosion of metallic nickel in aerated 0.5 kmol tn sodium sulfate solution as a function of pH and inserted sketches of its polarization curves in acidic and basic solutions [22] VENi = the corrosion rate of nickel. 

FIGURE 22.24 Anodic polarization curves for passivation and transpassivation of metallic iron and nickel in 0.5 kmol m-3 sulfuric acid solution with inserted sketches for electronic energy diagrams of passive films [32] /ip = passivation potential, TP = transpassivation potential, fb = flat band potential, /Fe = anodic dissolution current of metallic iron, Nl = anodic dissolution current of metallic nickel, and io2 — anodic oxygen evolution current. 

Anodic polarization curves determined potentiostatically for three low index faces cut from a nickel monocrystal grown paral-N H2S04 at 22-23 °C. Redrawn from Ref 15... 

Polarization curves for nickel-rich nickel-chromium alloys in 1 N H2SO4 are shown in Fig. 5.27 and for chromium-rich alloys in Fig. 5.28... 

Anodic polarization curves for nickel-chromium alloys in 1 N H2S04. Redrawn from Ref 1 3... 

Ref 13). These alloys are face-centered-cubic solid solutions from 0 to approximately 40 wt% chromium and body-centered-cubic from approximately 90 to 100 wt% chromium. The intermediate alloys are two-phase structures. The progressive influence of chromium in nickel in decreasing Epp, icrit, and ip is evident, and, hence the higher chromium alloys are more easily passivated. An exception is that the polarization curve for pure chromium occurs at larger current densities than for the 90 wt% chromium alloy. 

The effect of pH on the polarization of iron is shown in Fig. 5.6. The effect ofpH on the polarization of type 304 stainless steel (nominally 18 to 20 wt% Cr, 8 to 10.5 wt%Ni, 0.08 wt% C maximum) in environments based on 1 M Na2SC>4 with additions of H2SO4 and NaOH to control the pH is shown in Fig. 5.31 (Ref 28). The influence of chromium and nickel in moving the anodic polarization curve of iron to lower current densities persists over the indicated pH range with the corrosion rates being very low for pH >4.0. 

The approximate anodic polarization curves for iron, nickel, chromium, and titanium in 1 N H2SO4 are shown in Fig. 5.42. The cathodic reactions are for the environments shown and are representative of curves obtained on platinum. Since they may be displaced significantly when the reactions occur on the other metal surfaces, particularly the shift of the oxygen curves to lower potentials and current densities, the following discussion is qualitative. The conclusions drawn, however, are consistent with observations on the actual metal/environment systems. 

In deaerated 1 N H2SO4 (pH = 0.56), hydrogen-ion reduction is the cathodic reaction with the cathodic polarization curve intersecting the iron, nickel, and chromium curves in the active potential region. Hence, active corrosion occurs with hydrogen evolution, and the corrosion rates would be estimated by the intersections of the curves. The curves predict that the titanium will be passivated. However, the position ofthe cathodic hydrogen curve relative to the anodic curves for titanium and chromium indicates that if the exchange current density for the hydro-... 

The sequence of reactions involved in the overall reduction of nitric acid is complex, but direct measurements confirm that the acid has a high oxidation/reduction potential, -940 mV (SHE), a high exchange current density, and a high limiting diffusion current density (Ref 38). The cathodic polarization curves for dilute and concentrated nitric acid in Fig. 5.42 show these thermodynamic and kinetic properties. Their position relative to the anodic curves indicate that all four metals should be passivated by concentrated nitric acid, and this is observed. In fact, iron appears almost inert in concentrated nitric acid with a corrosion rate of about 25 pm/year (1 mpy) (Ref 8). Slight dilution causes a violent iron reaction with corrosion rates >25 x 1()6 pm/year (106 mpy). Nickel also corrodes rapidly in the dilute acid. In contrast, both chromium and titanium are easily passivated in dilute nitric acid and corrode with low corrosion rates. 

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... 

The major alloying element contributing to resistance to pitting corrosion in iron- and nickel-base alloys is chromium. The effect of chromium in reducing both the critical current density and the passivating potential of iron in 1 N H2S04 is shown by the polarization curves of... 

Fig. 21 Polarization curve of pure nickel in deaerated 1 N H2SO4 at 25 °C [29].

A regime of simultaneous dissolution has also been found for Cu—Ni alloys in acidic chloride solutions. Rotating ring-disk electrode studies revealed an apparent Tafel region of the alloy and component polarization curves with mixed mass transfer and kinetic rate control [44, 45]. For a CugoNiio alloy, the kinetic parameters again indicate a coupling of the copper and nickel partial currents under steady state conditions [44]. 

A schematic summary of the alloying metals that affect the anodic polarization curve of stainless steel is shown in Fig. 4.16. The addition of 8% nickel to an alloy containing 18% chromium forms austenitic structure SS Type 304. The addition of Mn and N increases the stability of austenitic steel. The chromium content of stainless steel affects the anodic polarization curves as shown in Fig. 4.16. Nickel promotes repassivation in a corrosive environment, but concentrations higher than 30% reduces the passivation current, the critical current density, and increases the critical pitting potential. Nitrogen... 

K. Osozawa, H.. Engel, The anodic polarization curves of iron-nickel-chromium alloys, Corros. Sci. 6 (1966) 389-393. 

Figure 6.14. Values of critical and passive current densities obtained from potentiostatic anodic polarization curves for copper-nickel alloys in N H2SO4, 25°C [42]. (Reproduced with permission. Copyright 1961, The Electrochemical Society.)...

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