Oxide films stresses

Recently Perusich and Alkire [105] have proposed a mathematical model to determine the reaction and transport between liquid microjets and a reactive solid surface. Conditions were established under which oxide depassivation and repassivation occurs as a function of ultrasonic intensity, surface film thickness, and fluid microjet surface coverage. The model was based on the concept that cavitation induces sufficient momentum and mass transfer rates (water hammer pressures as described earlier) at a surface to create oxide film stresses leading to depassivation. The model was used to evaluate experimental data on the corrosion behavior of iron in sulfuric acid [106,107], Focused ultrasound was used to investigate processes that influence depassivation and repassivation phenomena on pure and cast iron in 2N H2S04 at two ultrasound frequencies and at power intensities of up to 7.8 kW/cm2. 

Under cyclic or repeated stress conditions, rupture of protective oxide films that prevent corrosion takes place at a greater rate than that at which new protec tive films can be formed. Such a situation frequently resiilts in formation of anodic areas at the points of rupture these produce pits that serve as stress-concentration points for the origin or cracks that cause ultimate failure. 

Because oxides are usually quite brittle at the temperatures encountered on a turbine blade surface, they can crack, especially when the temperature of the blade changes and differential thermal contraction and expansion stresses are set up between alloy and oxide. These can act as ideal nucleation centres for thermal fatigue cracks and, because oxide layers in nickel alloys are stuck well to the underlying alloy (they would be useless if they were not), the crack can spread into the alloy itself (Fig. 22.3). The properties of the oxide film are thus very important in affecting the fatigue properties of the whole component. 

We said in Chapter 21 that all metals except gold have a layer, no matter how thin, of metal oxide on their surfaces. Experimentally, it is found that for some metals the junction between the oxide films formed at asperity tips is weaker in shear than the metal on which it grew (Fig. 25.4). In this case, sliding of the surfaces will take place in the thin oxide layer, at a stress less than in the metal itself, and lead to a corresponding reduction in x to a value between 0.5 and 1.5. 

Oxide films formed at low temperatures are initially continuous and amorphous, but may undergo local crystallisation with the incorporation of the oxide islands , a process that is facilitated by water, heat, high electric fields and mechanical stress... 

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 )...

Many of the alloys of copper are more resistant to corrosion than is copper itself, owing to the incorporation either of relatively corrosion-resistant metals such as nickel or tin, or of metals such as aluminium or beryllium that would be expected to assist in the formation of protective oxide films. Several of the copper alloys are liable to undergo a selective type of corrosion in certain circumstances, the most notable example being the dezincification of brasses. Some alloys again are liable to suffer stress corrosion by the combined effects of internal or applied stresses and the corrosive effects of certain specific environments. The most widely known example of this is the season cracking of brasses. In general brasses are the least corrosion-resistant of the commonly used copper-base alloys. 

It is hardly surprising that the preparation of surfaces of plain specimens for stress-corrosion tests can sometimes exert a marked influence upon results. Heat treatments carried out on specimens after their preparation is otherwise completed can produce barely perceptible changes in surface composition, e.g. decarburisation of steels or dezincification of brasses, that promote quite dramatic changes in stress-corrosion resistance. Similarly, oxide films, especially if formed at high temperatures during heat treatment or working, may influence results, especially through their effects upon the corrosion potential. 

The rate of oxidation increases with temperature. Oxygen diffusion becomes more rapid, the oxide film becomes thicker and eventually cracks and spalls off due to internal stress. Oxidation then becomes continuous and rapid. 

The mechanism of the EEF polarity dependence of the micro-bubble emerging is believed to be that the electrolysis of water molecules absorbed plays an important role. The deposited Cr layer is susceptible to be oxidized, and cracks tend to form and propagate due to the interfacial stress between the oxidized film and the glass disk, resulting in the damage of the electrode. 

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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