Passivating oxide

The protective quality of the passive film is detennined by the ion transfer tlirough the film as well as the stability of the film with respect to dissolution. The dissolution of passive oxide films can occur either chemically or electrochemically. The latter case takes place if an oxidized or reduced component of the passive film is more soluble in the electrolyte than the original component. An example of this is the oxidative dissolution of CrjO ... 

Niobium is used as a substrate for platinum in impressed-current cathodic protection anodes because of its high anodic breakdown potential (100 V in seawater), good mechanical properties, good electrical conductivity, and the formation of an adherent passive oxide film when it is anodized. Other uses for niobium metal are in vacuum tubes, high pressure sodium vapor lamps, and in the manufacture of catalysts. 

Tantalum is not resistant to substances that can react with the protective oxide layer. The most aggressive chemicals are hydrofluoric acid and acidic solutions containing fluoride. Fuming sulfuric acid, concentrated sulfuric acid above 175°C, and hot concentrated aLkaU solutions destroy the oxide layer and, therefore, cause the metal to corrode. In these cases, the corrosion process occurs because the passivating oxide layer is destroyed and the underlying tantalum reacts with even mild oxidising agents present in the system. 

A critical issue is the stabiUty of the hydride electrode in the cell environment. A number of hydride formulations have been developed. Table 5 shows hydride materials that are now the focus of attention. Most of these are Misch metal hydrides containing additions of cobalt, aluminum, or manganese. The hydrides are prepared by making melts of the formulations and then grinding to fine powers. The electrodes are prepared by pasting and or pressing the powders into metal screens or felt. The additives are reported to retard the formation of passive oxide films on the hydrides. 

At high temperature, siUcon carbide exhibits either active or passive oxidation behavior depending on the ambient oxygen potential (65,66). When the partial pressure of oxygen is high, passive oxidation occurs and a protective layer of Si02 is formed on the surface. 

A fresh surface of siUcon carbide is thus constantiy being exposed to the oxidizing atmosphere. Active oxidation takes place at and below approximately 30 Pa (0.23 mm Hg) oxygen pressure at 1400°C (66). Passive oxidation is determined primarily by the nature and concentration of impurities (67). 

Impurities in a corrodent can be good or bad from a corrosion standpoint. An impurity in a stream may act as an inhibitor and actually retard corrosion. However, if this impurity is removed by some process change or improvement, a marked rise in corrosion rates can result. Other impurities, of course, can have very deleterious effec ts on materials. The chloride ion is a good example small amounts of chlorides in a process stream can break down the passive oxide film on stainless steels. The effects of impurities are varied and complex. One must be aware of what they are, how much is present, and where they come from before attempting to recommena a particular material of construction. 

There is often a period before corrosion starts in a crevice in passivating metals. This so-called incubation period corresponds to the time necessary to establish a crevice environment aggressive enough to dissolve the passive oxide layer. The incubation period is well known in stainless steels exposed to waters containing chloride. After a time period in which crevice corrosion is negligible, attack begins, and the rate of metal loss increases (Fig. 2.8). 

Fig. 24.2. Some sacrificial materials do not work because they carry a passivating oxide layer.

Figure 2-11 shows weight loss rate-potential curves for aluminum in neutral saline solution under cathodic protection [36,39]. Aluminum and its alloys are passive in neutral waters but can suffer pitting corrosion in the presence of chloride ions which can be prevented by cathodic protection [10, 40-42]. In alkaline media which arise by cathodic polarization according to Eq. (2-19), the passivating oxide films are soluble ... 

On the other hand, pit initiation which is the necessary precursor to propagation, is less well understood but is probably far more dependent on metallurgical structure. A detailed discussion of pit initiation is beyond the scope of this section. The two most widely accepted models are, however, as follows. Heine, etal. suggest that pit initiation on aluminium alloys occurs when chloride ions penetrate the passive oxide film by diffusion via lattice defects. McBee and Kruger indicate that this mechanism may also be applicable to pit initiation on iron. On the other hand, Evans has suggested that a pit initiates at a point on the surface where the rate of metal dissolution is momentarily high, with the result that more aggressive anions... 

The process of formation of a passivating oxide film is an anodic one the driving force for its formation is raised by raising the potential anodically... 

Formation of the first layer (a monolayer) of passivating oxide film on a denuded metal surface occurs very simply by the loss of protons from the adsorbed intermediate oxidation products, such intermediates being common to both dissolution and passivation processes . Thus for example, the first oxidative step in the anodic oxidation of nickel is the formation of the unstable adsorbed intermediate NiOH by... 

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