Oxide layers, passivating

The production of corrosion-resistant materials hy alloying is well established, hut the mechanisms are noi lull) understood. It is known, of course, that elements like chromium, mckcl. titanium, and aluminum depend for their corrosion resistance upon a tenacious surface oxide layer (passive film). Alloying elements added for the purpose of passivation must be in solid solution. The potential of ion implantation is promising because restrictions deriving from equilibrium phase diagrams frequently do not applv li e., concentrations of elements beyond tile limits of equilibrium solid solubility might he incorporated). This can lead to heretofore unknown alloyed surfact-s which are very corrosion resistant... 

Stainless steels are examples of alloy steels, i.e. ones that contain a J-block metal in addition to carbon. Stainless steels have a significant content of the alloy metal and are of high commercial value because of their high resistance to corrosion. All contain a minimum of 10.5% (by mass) of chromium and the resistance to corrosion arises from the formation of a thin layer of Cr203 ( 13 000 pm thick) over the surface of the steel. The oxide layer passivates (see Section 9.4) the steel and is self-repairing, i.e. if some of the oxide coating is scratched off, further oxidation of the chromium in the steel necessarily repairs the wound . A further property that makes stainless steels commercially important is that they can be polished to satin or mirror finishes and this is easily appreciated in the ranges of stainless steel cutlery available to the consumer. 

Data on the chemistry and structure of thin oxide layers (passive films) produced by anodic polarization of metallic electrodes are necessary to understand and predict the properties of these films, in particular their corrosion resistance. There are now many available data on the chemical composition of passive films formed on metals and alloys. Surfece chemical analysis techniques have been, and still are, very useful to obtain such data. In sharp contrast, there is a lack of data on the structure of passive films. This is in part due to the difficulty of any structural analysis of very thin films on... 

When the passivation potential Upas is exceeded, the corrosion current value 1a drops to very low levels and metal dissolution practically ceases. In practical terms, the corrosion current then remains at a constant low level even as the potential continues to increase. The metal surface is protected by a very thin, invisible oxide layer (passivation layer). 

Because the metal dissolution is an anodic process, for example, Fe(s) Fe +(aq) + 2e , the current of the process is assumed to be positive. When potential increases from Mez+zMe lo f (passivation or Flade potential), the current is increasing exponentially due to the electron transfer reaction, for example, Fe(s) -> Fe +(aq) + 2e", and can be described using Tafel s equation. At a E the formation of an oxide layer (passive film) starts. When the metal surface is covered by a metal oxide passive film (an insulator or a semiconductor), the resistivity is sharply increasing, and the current density drops down to the rest current density, 7r. This low current corresponds to a slow growth of the oxide layer, and possible dissolution of the metal oxide into solution. In the region of transpassivation, another electrochemical reaction can take place, for example, H20(l) (l/2)02(g) + 2H+(aq) + 2e, or the passive film can be broken down due to a chemical interaction with environment and mechanical instability. Clearly, a three-electrode cell and a potentiostat should be used to obtain the current density-potential curve shown in Figure 9.3. 

It should be mentioned that a free metal dissolution is not observed very often in practice. Usually the metal is covered by a film of corrosion products like oxide layers, passive films, well-soluble or weakly soluble salt layers, adsorption layers, and organic films, which have... 

Strong oxidising acids, for example hot concentrated sulphuric acid and nitric acid, attack finely divided boron to give boric acid H3CO3. The metallic elements behave much as expected, the metal being oxidised whilst the acid is reduced. Bulk aluminium, however, is rendered passive by both dilute and concentrated nitric acid and no action occurs the passivity is due to the formation of an impervious oxide layer. Finely divided aluminium does dissolve slowly when heated in concentrated nitric acid. 

Nitric acid reacts with all metals except gold, iridium, platinum, rhodium, tantalum, titanium, and certain alloys. It reacts violentiy with sodium and potassium to produce nitrogen. Most metals are converted iato nitrates arsenic, antimony, and tin form oxides. Chrome, iron, and aluminum readily dissolve ia dilute nitric acid but with concentrated acid form a metal oxide layer that passivates the metal, ie, prevents further reaction. 

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. 

The corrosion resistance imparted to tantalum by the passivating surface thermal oxide layer makes the metal inert to most ha2ards associated with metals. Tantalum is noncorrosive in biological systems and consequently has a no chronic health ha2ard MSDS rating. 

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.

Certainly a thermodynamically stable oxide layer is more likely to generate passivity. However, the existence of the metastable passive state implies that an oxide him may (and in many cases does) still form in solutions in which the oxides are very soluble. This occurs for example, on nickel, aluminium and stainless steel, although the passive corrosion rate in some systems can be quite high. What is required for passivity is the rapid formation of the oxide him and its slow dissolution, or at least the slow dissolution of metal ions through the him. The potential must, of course be high enough for oxide formation to be thermodynamically possible. With these criteria, it is easily understood that a low passive current density requires a low conductivity of ions (but not necessarily of electrons) within the oxide. 

Hitzig et al. have produced a simplified model of the aluminium oxide layer(s) to explain impedance data of specimens prepared under different layer formation and sealing conditionsThe model also gives consideration to the formation of active and passive pits in the oxide layer. Shaw et al. have shown that it is possible to electrochemically incorporate molybdenum into the passive film which, as previously noted, improves the pitting resistance. 

Turning now to the acidic situation, a report on the electrochemical behaviour of platinum exposed to 0-1m sodium bicarbonate containing oxygen up to 3970 kPa and at temperatures of 162 and 238°C is available. Anodic and cathodic polarisation curves and Tafel slopes are presented whilst limiting current densities, exchange current densities and reversible electrode potentials are tabulated. In weak acid and neutral solutions containing chloride ions, the passivity of platinum is always associated with the presence of adsorbed oxygen or oxide layer on the surface In concentrated hydrochloric acid solutions, the possible retardation of dissolution is more likely because of an adsorbed layer of atomic chlorine ... 

Since the natural passivity of aluminium is due to the thin film of oxide formed by the action of the atmosphere, it is not unexpected that the thicker films formed by anodic oxidation afford considerable protection against corrosive influences, provided the oxide layer is continuous, and free from macropores. The protective action of the film is considerably enhanced by effective sealing, which plugs the mouths of the micropores formed in the normal course of anodising with hydrated oxide, and still further improvement may be afforded by the incorporation of corrosion inhibitors, such as dichromates, in the sealing solution. Chromic acid films, in spite of their thinness, show good corrosion resistance. 

The corrosion current due to diffusion of metal ions through the passivating film, and dissolution of metal ions at the oxide-solution interface. Clearly, the smaller this current, the more protective is the oxide layer. 

Thus inhibitive anions can retard the dissolution of both the T-FejO, and the magnetite layers of the passivating oxide layer on iron. This has the dual effect of preventing breakdown of an existing oxide film and also of facilitating the formation of a passivating oxide film on an active iron surface, as discussed in the previous section. 

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