Breakdown oxide film

Highly protective layers can also fonn in gaseous environments at ambient temperatures by a redox reaction similar to that in an aqueous electrolyte, i.e. by oxygen reduction combined with metal oxidation. The thickness of spontaneously fonned oxide films is typically in the range of 1-3 nm, i.e., of similar thickness to electrochemical passive films. Substantially thicker anodic films can be fonned on so-called valve metals (Ti, Ta, Zr,. ..), which allow the application of anodizing potentials (high electric fields) without dielectric breakdown. 

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. 

An especially insidious type of corrosion is localized corrosion (1—3,5) which occurs at distinct sites on the surface of a metal while the remainder of the metal is either not attacked or attacked much more slowly. Localized corrosion is usually seen on metals that are passivated, ie, protected from corrosion by oxide films, and occurs as a result of the breakdown of the oxide film. Generally the oxide film breakdown requires the presence of an aggressive anion, the most common of which is chloride. Localized corrosion can cause considerable damage to a metal stmcture without the metal exhibiting any appreciable loss in weight. Localized corrosion occurs on a number of technologically important materials such as stainless steels, nickel-base alloys, aluminum, titanium, and copper (see Aluminumand ALUMINUM ALLOYS Nickel AND nickel alloys Steel and Titaniumand titanium alloys). 

Fig. 21.5 Breakdown of oxide films, leading to linear oxidation behaviour.

Fig. 1.45 Breakdown of oxide film leading to a pit and crack when a high-strength steel is subjected to a tensile stress in a chloride solution (after Brown )...

As copper is not an inherently reactive element, it is not surprising that the rate of corrosion, even if unhindered by films of insoluble corrosion products, is usually low. Nevertheless, although the breakdown of a protective oxide film on copper is not likely to lead to such rapid attack as with a more reactive metal such as, say, aluminium, in practice the good behaviour of copper (and more particularly of some of its alloys) often depends to a considerable extent on the maintenance of a protective film of oxide or other insoluble corrosion product. 

It is somewhat less corrosion resistant than tantalum, and like tantalum suffers from hydrogen embrittlement if it is made cathodic by a galvanic couple or an external e.m.f., or is exposed to hot hydrogen gas. The metal anodises in acid electrolytes to form an anodic oxide film which has a high dielectric constant, and a high anodic breakdown potential. This latter property coupled with good electrical conductivity has led to the use of niobium as a substrate for platinum-group metals in impressed-current cathodic-protection anodes. 

As indicated above, when a positive direct current is impressed upon a piece of titanium immersed in an electrolyte, the consequent rise in potential induces the formation of a protective surface film, which is resistant to passage of any further appreciable quantity of current into the electrolyte. The upper potential limit that can be attained without breakdown of the surface film will depend upon the nature of the electrolyte. Thus, in strong sulphuric acid the metal/oxide system will sustain voltages of between 80 and 100 V before a spark-type dielectric rupture ensues, while in sodium chloride solutions or in sea water film rupture takes place when the voltage across the oxide film reaches a value of about 12 to 14 V. Above the critical voltage, anodic dissolution takes place at weak spots in the surface film and appreciable current passes into the electrolyte, presumably by an initial mechanism involving the formation of soluble titanium ions. 

By virtue of the high breakdown potential of the oxide film (approximately 155 V in sea water and 280 V in low conductivity water of pH = 7) tantalum has found use as a substrate for platinum in impressed-current cathodic-protection anodes, which can be used at high impressed voltages (50 V) and high current densities. However, because of its lower cost, niobium is preferred for systems that have to operate at high voltages... 

Aqueous environments Neutral chloride solutions do not corrode titanium alloys at ambient temperatures, and smooth statically loaded specimens of susceptible alloys do not exhibit failure. In order to nucleate cracking it appears probable that the protective oxide film on alloys must be destroyed and its repair must not occur. If this breakdown occurs then cracking is observed in susceptible alloys. Consequently, the type of test and the type of specimen employed in any selected test are both important considerations, particularly in alloys exhibiting low susceptibility. 

It is a valve metal and when made anodic in a chloride-containing solution it forms an anodic oxide film of TiOj (rutile form), that thickens with an increase in voltage up to 8-12 V, when localised film breakdown occurs with subsequent pitting. The TiOj film has a high electrical resistivity, and this coupled with the fact that breakdown can occur at the e.m.f. s produced by the transformer rectifiers used in cathodic protection makes it unsuitable for use as an anode material. Nevertheless, it forms a most valuable substrate for platinum, which may be applied to titanium in the form of a thin coating. The composite anode is characterised by the fact that the titanium exposed at discontinuities is protected by the anodically formed dielectric Ti02 film. Platinised titanium therefore provides an economical method of utilising the inertness and electronic conductivity of platinum on a relatively inexpensive, yet inert substrate. 

The formation of deposits on platinised anodes can cause anode degradationThus dissolved impurities present in water which are liable to oxidation to insoluble oxides, namely Mn, Fe, Pb and Sn, can have a detrimental effect on anode life. In the case of MnOj films it has been stated that MnOj may alter the relative proportions of Cl, and O, produced and thus increase the Pt dissolution rate Fe salts may be incorporated into the TiO, oxide film and decrease the breakdown potential or form thick sludgy deposits. The latter may limit electrolyte access and iead to the development of localised acidity, at concentrations sufficient to attack the underlying substrate . 

Platinised-titanium anodes may also be used in soils when surrounded by a carbonaceous backfill. Warne and Berkeley " have investigated the performance of platinised-titanium anodes in carbonaceous backfills and conclude that the anodes may be successfully operated in this environment at a current density of up to 200 AmThis also supplements the findings of Lewis, who states that platinised-titanium anodes may be used in carbonaceous backfill without breakdown of the titanium oxide film. Success with platinised-titanium anodes has been reported with anodes operating at a few tens of Am and failures of anodes have often been attributed to operation at high current densities . 

There have been instances reported in the literature where the breakdown potential for Nb and Ta in seawater has been found to be lower than the generally accepted value of 120 V, with reported values in extreme instances as low as 20- V . This has been attributed to contamination of the niobium surface from machining operations, grit blasting or traces of copper lubricant used in anode manufacture. These traces of impurities, by becoming incorporated in the oxide film, decrease its dielectric properties and thus account for the lower breakdown voltage. Careful control of surface contamination in the manufacture of platinised niobium is therefore essential to minimise the lowering of the breakdown potential of niobium. 

The critical breakdown potential, which is the positive potential limit of stability of the oxide film. At this potential and more positive potentials, the oxide film is unstable with respect to the action of anions, especially halide ions, in causing localised rupture and initiating pitting corrosion. 

All of these three properties of the oxide films on metals are influenced by the anion composition and pH of the solution. In addition the potential of the metal will depend on the presence of oxidising agents in the solution. Inhibition of corrosion by anions thus requires an appropriate combination of anions, pH and oxidising agent in the solution so that the oxide film on the metal is stable (the potential then lying between the Flade potential and the breakdown potential), and protective (the corrosion current through the oxide being low). 

The corrosion of iron (or steel) can be inhibited by the anions of most weak acids under suitable conditions " . However, other anions, particularly those of strong acids, tend to prevent the action of inhibitive anions and stimulate breakdown of the protective oxide film. Examples of such aggressive anions are the halides, sulphate, nitrate, etc. Brasher has shown that, in general, most anions exhibit some inhibitive and some aggressive behaviour towards iron. The balance between the inhibitive and aggressive properties of a specific anion depends on the following main factors (which are themselves interdependent). 

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. 

The relative importance of these functions also depends to a considerable extent on the solution conditions. Under favourable conditions of pH, oxidising power and aggressive anion concentration in the solution, Function 1 is probably effective in preventing film breakdown. Under unfavourable conditions for inhibition, localised breakdown will occur at weak points in the oxide film, and Functions 2 and 3 become important in repairing the oxide film. 

Albella, J. M. Electric Breakdown in Anodic Oxide Films 23... 

Electric Breakdown in Anodic Oxide Films Parkhutik, V. P. Albella, J. M. Martinez-Duart, J. M. 23... 

Electric Breakdown in Anodic Oxide Films Physics and Applications of Semiconductor Electrodes Covered with Metal Clusters Analysis of the Capacitance of the Metal-Solution Interface. Role of the Metal and the Metal-Solvent Coupling Automated Methods of Corrosion Measurement... 

There are also models assuming the electrostrictive input of incorporated anions into the breakdown initiation,285,299 ionic drift models,300 and many others reviewed elsewhere.283,293 However, the majority of specialists agree that further work is necessary in order to properly understand the physics of the electric breakdown in growing oxide films and that caused by electric stress in thin-film structures. 

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