Oxide layers stresses

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. 

Fortunately the oxidation of many metals takes place by the diffusion of the metal cation . This flux is outwards through the oxide layer, and the work of adhesion" enables the loss of metal to be compensated for by a drift of the oxide towards the metal (Fig. 1.81). Thus the stresses set up in the maintenance of oxide/metal contact are compressive and, as such, can be more readily withstood by most oxides. Nevertheless, it is these general movements of the oxide scale which are ultimately responsible for discontinuities in the majority of cases and it is appropriate to discuss transport-induced flows before proceeding any further. 

In some cases the number of oxide layers can be related directly to the number of breaks in the curve and there is then no doubt that the acceleration derives from repetitive stress-induced oxide cracking. 

The rigidity of the y axis prevents the development of spherical surfaces for all but very small displacements. Morton suggests that the limit is reached when the displacement is equal to the metal thickness. This condition was satisfied in the high-temperature studies of Appleby and Tylecote and spherical doming of the disc specimen occurred. When the oxide is not very thin compared with the metal both the moduli for oxide and metal must be considered. Stringer" , in his excellent review of stress generation and relief in oxide layers, quotes a corrected formula, originally due to Brenner and Senderoff ... 

The reduced oxidation near sample corners is related to these stress effects, either by retarded diffusion or modified interfacial reactionsManning described these stresses in terms of the conformational strain and distinguished between anion and cation diffusion, and concave and convex surfaces. He defined a radial vector M, describing the direction and extent of displacement of the oxide layer in order to remain in contact with the retreating metal surface, where ... 

Under thermal cycling conditions, the principal source of stress within the oxide scale is the temperature change . Christl et have noted that, when cooling 2.25%Cr-l%Mo steel from 600°C in air, compressive stresses build up in the haematite, whilst tensile stresses build up in the magnetite and spinel layers. This arises because the thermal expansion coefficients of the individual oxide layers increase in the order a metal < a spinel < a magnetite < a haematite . ... 

Figure 23. Artificial muscle formed by a three-layer polypyrrole-nonconducting tape-polypyrrole. The consumed charge works two times in this device when polypyrrole I is oxidized (anodic process), pushing the free end of the layer, polypyrrole II is reduced (cathodic process), trailing the layer. Stresses at the polymer/polymer interfaces are summarized in the box. (Reprinted from Handbook of Organic Conductive Molecules and Polymers, H. S.Nalwa,ed., Vol. 4,1997, Figs. 10.13,10.15a, 10.18,10.36. Reproducedwithpermission of John Wiley Sons, Ltd., Chichester, UK.)...

Experiments done in the absence of an external stress showed that the effects of degradation crosslinking are significant at relatively short times of UV exposure, and confirmed that the photodegradation is essentially in the surface layers. The oxidized layer thickness appeared to remain more or less constant after a certain exposure. 

The thermal expansion coefficient of silicon is approximately seven times larger than that of Si02, as given in Table 2. When Si02 is deposited, typically at temperatures of several hundred degrees C, an in-plane compressive stress develops in the oxide layer as the Si wafer is cooled by AT to room temperature. For a uniform 2-dimensional thin film deposited on a substrate, the in-plane stress obtained from Equation 2 is ... 

Although the titanium oxide layer at the surface of the nitinol is highly biocompatible and protects the underlying substrate from electrochemical corrosion, the titanium oxide layer itself is mechanically very brittle. Under mechanical stress, such as the shear of blood flow in the aorta or under the bending moments of aortic pulsations, the titanium oxide surface layer can fracture, exposing the underlying metal to corrosion. Not only is corrosion undesirable in terms of biocompatibility (i.e., leaching of nickel and its... 

In an optical micrograph of a commercially available nitinol stent s surface examined prior to implantation, surface craters can readily be discerned. These large surface defects are on the order of 1 to 10 p.m and are probably formed secondary to surface heating during laser cutting. As mentioned above, these defects link the macro and micro scales because crevices promote electrochemical corrosion as well as mechanical instability, each of which is linked to the other. Once implanted, as the nitinol is stressed and bent, the region around the pits experiences tremendous, disproportionate strain. It is here that the titanium oxide layer can fracture and expose the underlying surface to corrosion (9). 

If local stresses exceed the forces of cohesion between atoms or lattice molecules, the crystal cracks. Micro- and macrocracks have a pronounced influence on the course of chemical reactions. We mention three different examples of technical importance for illustration. 1) The spallation of metal oxide layers during the high temperature corrosion of metals, 2) hydrogen embrittlement of steel, and 3) transformation hardening of ceramic materials based on energy consuming phase transformations in the dilated zone of an advancing crack tip. 

Figure 3. XPS spectra of a silicon sample containing ca. 30 nm thick oxide. A strip of gold metal is tied for referencing under different voltage stress. The inset displays the measured binding energy difference between the Si2p of the oxide layer (Si4+), and the Au4f of the gold metal. Zero Charge Point (ZCP) is obtained at ca. +1V stress.

Figure 8. XPS spectra of the Si2p-Pt4f region of silicon sample containing ca. 6 nm thermal oxide layer, and also containing Pt particles deposited from an aqueous solution, and reduced by x-rays without and under +10 and -10V external voltage stress. The figure also contains spectra recorded with 0 to +10V pulses at 50, and 0.5 Hz, 0 to -10V pulses again at 50 and 0.5 Hz.

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