Passive films nickel

The stainless steels contain appreciable amounts of Cr, Ni, or both. The straight chrome steels, types 410, 416, and 430, contain about 12, 13, and 16 wt % Cr respectively. The chrome—nickel steels include type 301 (18 wt % Cr and 9 wt % Ni), type 304 (19 wt % Cr and 10 wt % Ni), and type 316 (19 wt % Cr and 12 wt % Ni). Additionally, type 316 contains 2—3 wt % Mo which gready improves resistance to crevice corrosion in seawater as well as general corrosion resistance. AH of the stainless steels offer exceptional improvement in atmospheric conditions. The corrosion resistance results from the formation of a passive film and, for this reason, these materials are susceptible to pitting corrosion and to crevice corrosion. For example, type 304 stainless has very good resistance to moving seawater but does pit in stagnant seawater. 

It is known that thin (-20 A) passive films form on iron, nickel, chromium, and other metals. In s ressive environments, these films provide excellent corrosion protection to the underlying metal. The structure and composition of passive films on iron have been investigated through iron K-edge EXAFS obtained under a variety of conditions, yet there is still some controversy about the exact nature of... 

The passive films formed by the addition of sufficient amounts of valve metals to amorphous nickel-valve-metal alloys are exclusively composed of valve-metal oxyhydroxides or oxides such as TaOjCOH) , Nb02(OH) or TajO,. Consequently, amorphous alloys containing strongly passivating elements, such as chromium, niobium and tantalum, have a very high ability... 

Most authorities nowadays accept the view that passivity of nickel, as of most other metals, is due to the formation of a film of oxide or hydrated... 

In acidic solutions the film has been reported to be hydrated nickel oxyhydroxide, NiOy(OH)2 2y. MH2O in which y is greater in the passive film than in the pre-passive film formed in the active region . In neutral solutions films consisting of NiO and Ni(OH)2 possibly with some NiO have been described. In alkaline solutions NifOHlj has been reported . 

Nickel and nickel alloys possess good resistance to sea-water in conditions where the protective properties of the passive film are fully maintained. As pointed out above, Ni-30 Cu Alloy 400, in contrast to its behaviour in acidic solution, normally forms a protective film in neutral and alkaline environments, including sea-water this alloy and its age hardening variant... 

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... 

When stainless steel is struck the passive film is reduced and an adherent flash of nickel forms on the active metal surface. Deposition is continued in a normal bath. 

Figure 39. Current-time variation in nickel pitting dissolution in NaCl solution.89,91 1, double-layer charging current 2, fluctuation-diffusion current 3, minimum dissolution current 4, pit-growth current (Reprinted from M. Asanuma andR. Aogaki, Nonequilibrium fluctuation theory on pitting dissolution. II. Determination of surface coverage of nickel passive film, J. Chem. Phys. 106, 9938, 1997, Fig. 2. Copyright 1997, American Institute of Physics.)...

After a constant potential step beyond the pitting potential is applied to a nickel electrode in NaCl solution, the current transient shown in Fig. 39 is observed. The J vs. 1/VT plot according to Eq. (104) is shown in Fig. 40. From the linear portion corresponding to Eq. (104), the slope of the plot can be described as a function of the surface coverage 6 of the passive film in the following... 

The probes are 1-mm nickel rods with square ends. They are powered by 100-V dc power supplies. The positive side of the power supply is connected to the cell body. (This makes the probes cathodic to the case.) The control modules have 12 M3 resistance so that when contact is made, less than 10 mA flows through the circuit this is not a dangerous current. (The use of a 12-V power supply and lower resistance modules did not reliably deliver a control signal when contact was made this may have been caused by the buildup of a passive film on the probe that was not cleared by the lower voltage.)... 

Froment and co-workers have employed reflexafs77 (reflection EXAFS) for studying passive films on iron78 and nickel.79 80 The experiment consists of measuring the ratio of the reflected and incident intensities as a function of energy. Although an EXAFS spectrum can be obtained from such a measurement, the process is somewhat involved since the reflectivity is a complex function... 

Mechanism 3 involves NiOH in at least three reactions, and Ni(OH)2 as the active Ni reactant in solution. Since increasing the concentration of the complex-ant(s) in solution will reduce the concentration of both unhydrolyzed and hydrolyzed metal ions, arguments of complexation cannot be readily employed to either support or discount this mechanism. However, it has been this author s experience in formulating electroless Co-P solutions with various complexants for Co2+ that improper complexation which results in even a faint precipitate of hydrolyzed cobalt ions yields an inactive electroless Co-P solution. Furthermore, anodic oxidation of hypo-phosphite at Ni anodes does not proceed at a significant rate under conditions where the surface is most probably covered with a passive film of nickel oxide [48], e.g. NiO.H20, which would be expected to oxidize the reducing agent via a cyclic redox mechanism. 

The transition from the active state to the passive state is the passivation, and the transition in the reverse direction is the activation or depassivation. The threshold of potential between the active and the passive states is called the passivation potential or the passivation-depassivation potential. Similarly, the transition from the passive state to the transpassive state is the transpassivation, and the critical potential for the transpassivation is called the transpassivation potential. Further, a superficial thin film formed on metals in the passive state is often called the passive film (or passivation film), the thickness of which is in the order of 1 to 5 nm on transition metals such as iron and nickel. 

In the case of nickel electrodes on which the passive film is a p-f pe nickel oxide (NiO), the energy gap ( 0.2 eV) between the valence band edge and the Fermi level at the flat band potential is small so that the transpassivation potential Etp is relatively close to the flat band potential as in Fig. 11-13. 

For metallic iron and nickel electrodes, the transpassive dissolution causes no change in the valence of metal ions during anodic transfer of metal ions across the film/solution interface (non-oxidative dissolution). However, there are some metals in which transpassive dissolution proceeds by an oxidative mode of film dissolution (Sefer to Sec. 9.2.). For example, in the case of chromium electrodes, on whidi the passive film is trivalent chromium oxide (CrgOj), the transpassive dissolution proceeds via soluble hexavalent chromate ions. This process can be... 

Fig. 16.6. Voltammetric curve for a metal that forms a passive film, e.g. nickel...

Passive films formed in aqueous solutions consist of an oxide or a mixture of oxides, usually in hydrated form. The oxide formed on some metals (e.g., Al, Ti, Ta, Nb) is an electronic insulator, while on other metals the passivating oxide film behaves like a semiconductor. Nickel, chromium, and their alloys with iron (notably the various kinds of stainless steel) can be readily passivated and, in fact, tend to be spontaneously passivated upon contact with water or moist air. It should be noted that passivation does not occur when chloride ions are introduced into the solution indeed a preexisting passive film may be destroyed. Many other ions are detrimental to passivity, such as Br, I, SO, and CIO, but chloride is the worst offender, because of its... 

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