Nickel alloys passive current densities

Because these variables have a very pronounced effect on the current density required to produce and also maintain passivity, it is necessary to know the exact operating conditions of the electrolyte before designing a system of anodic protection. In the paper and pulp industry a current of 4(KX) A was required for 3 min to passivate the steel surfaces after passivation with thiosulphates etc. in the black liquor the current was reduced to 2 7(X) A for 12 min and then only 600 A was necessary for the remainder of the process . From an economic aspect, it is normal, in the first instance, to consider anodically protecting a cheap metal or alloy, such as mild steel. If this is not satisfactory, the alloying of mild steel with a small percentage of a more passive metal, such as chromium, molybdenum or nickel, may decrease both the critical and passivation current densities to a sufficiently low value. It is fortunate that the effect of these alloying additions can be determined by laboratory experiments before application on an industrial scale is undertaken. 

Several experimental results support the adsorption mechanism for stationary conditions of the passive layer. Even the stationary passive current density depends on the composition of the electrolyte. For iron in 0.5 M H2SO4, the passive current density is 7 pA cm , whereas less than lpAcm is detected in 1 M HCIO4. From these observations, a catalysis for the transfer of Fe + from the passive layer to the electrolyte by S04 ions was concluded [55, 56]. Similarly, the dissolution Ni + from passive nickel and nickel base alloys is accelerated by organic acids hke formic acid and leads to a removal of NiO from the passive layer [57]. Additions of citrate to the electrolyte cause the thinning of passive layers on stainless steel and increase its Cr content [58]. Apparently Fe and Ni ions are complexed at the surface of the passive film, which causes an enhancement of their dissolution into the electrolyte. It should be mentioned that the dissolution of Cr " " apparently is not catalyzed by these anions and remains... 

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.)...

In acidic media, the metals iron, nickel and chromium have passivation current densities that increase in the order Cr < Ni < Fe. In Figure 6.11, the anodic polarization curves for the three metals in 0.5 M sulfuric acid (25 °C) are compared. Chromium has lower values of both ip and Ep than the other two metals. By alloying increasing amounts of chromium to steel one therefore improves the corrosion resistance. Experience shows that above a chromium concentration of 12 to 13%, a steel passivates spontaneously in contact with aerated water. It becomes "stainless", meaning it does not rust easily. Figure 6.12 gives the corrosion potential of different... 

Table 10.32 Effect on critical current density and passivation potential on alloying nickel with chromium in In and IOn H2SO4 both containing 0-5N K2SO4 (after Myers, Beck and Fontana")...

Electroplating passive alloys Another application of strike baths reverses the case illustrated in the previous example. The strike is used to promote a small amount of cathode corrosion. When the passivation potential of a substrate lies below the cathode potential of a plating bath, deposition occurs onto the passive oxide film, and the coating is non-adherent. Stainless steel plated with nickel in normal baths retains its passive film and the coating is easily peeled off. A special strike bath is used with a low concentration of nickel and a high current density, so that diffusion polarisation (transport overpotential) depresses the potential into the active region. The bath has a much lower pH than normal. The low pH raises the substrate passivation potential E pa, which theoretically follows a relation... 

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 extents of the passive potential regions have been reduced for all materials except pure chromium, and the curves for 90 and 100 wt% nickel indicate that an active-to-passive state transition no longer occurs. The magnitude of the influence of the chloride ions is emphasized by comparing the current densities for each alloy at 200 mV (SHE) with and without chloride ions present. 

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... 

The technique may be understood in terms of metallic passivity, i.e. the loss of chemical activity experienced by certain metals and alloys under particular environmental conditions as a result of surface film formation. Equations 15.2 and 15.3 suggest that the application of an anodic current to a metal should tend to increase metal dissolution and decrease hydrogen production. Metals that display passivity, such as iron, nickel chromium, titanium and their alloys respond to an anodic current by shifting their polarisation potential into the passive regon. Current densities required to initiate passivity are relatively high [Uhlig and Revie 1985] but the current density to maintain passivity are low, with a consequent reduction in power costs [Scully 1990]. 

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... 

The passivation of chromium begins more than 500 mV before that of iron and requires a considerably lower current density. The good passivation capability of chromium can be imparted to iron by alloying with <12% chromium. This forms the basis for the development of all stainless and acid resistance steels. Further improvement can be obtained by adding nickel, molybdenum, and copper to these alloys. 

A passive metal is one that is active in the Emf Series, but that corrodes nevertheless at a very low rate. Passivity is the property underlying the useful natural corrosion resistance of many structural metals, including aluminum, nickel, and the stainless steels. Some metals and alloys can be made passive by exposure to passivating environments (e.g., iron in chromate or nitrite solutions) or by anodic polarization at sufficiently high current densities (e.g., iron in H2SO4). 

Additions of chromium to nickel impart resistance to oxidizing conditions (e.g., HNO3 and H2Cr04) by supporting the passivation process. The critical minimum chromium content [4] obtained from critical current densities for anodic passivation in sulfuric acid is 14 wt.% Cr. These alloys are more sensitive than nickel to attack by CT and by HCl, and deep pits form when the alloys are... 

Those alloying additions which decrease icritical are effective in increasing the passivating tendency. Consider alloying additions of Mo, Ni, Ta and Cb to Ti and Cr. The critical current density of Ti and Cr is reduced on addition of Mo, Ni, Ta or Cb. The potential of the above elements is active and their rate of corrosion is low. Generally, those alloying elements are useful which show low corrosion rates at the active potentials. Alloying with metals which passivate more readily than the base metal reduces icritical and induces passivity. Elements, like chromium and nickel, which have a lower (critical and Epassive than iron, reduce the... 

Cobalt-base alloys. The corrosion behavior of pure cobalt has not been documented as extensively as that of nickel. The behavior of cobalt is similar to that of nickel, although cobalt possesses lower overall corrosion resistance. For example, the passive behavior of cobalt in 0.5 M sulfuric acid has been shown to be similar to that of nickel, but the critical current density necessary to achieve passivity is 14 times higher for the former. Several investigations have been carried out on binary cobalt-chromium alloys. In cobalt-base alloys, it has been found that as little as 10% chromium is sufficient to reduce the anodic current density necessary for passivation from 500 to 1 mA cm". For nickel, about 14% chromium is needed to reduce the passivating anodic current density to the same level. 

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