Oxide films Subject

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 )...

Chromium is the most effective alloying element to give resistance to oxidation, forming a tenacious oxide film. Chromium alloys should be specified for equipment subject to temperatures above 500°C in oxidising atmospheres. 

Even single metals, however, are subject to aqueous corrosion by essentially the same electrochemical process as for bimetallic corrosion. The metal surface is virtually never completely uniform even if there is no preexisting oxide film, there will be lattice defects (Chapter 5), local concentrations of impurities, and, often, stress-induced imperfections or cracks, any of which could create a local region of abnormally high (or low) free energy that could serve as an anodic (or cathodic) spot. This electrochemical differentiation of the surface means that local galvanic corrosion cells will develop when the metal is immersed in water, especially aerated water. 

Dye-sensitized solar cells (DSSCs) are photoelectrochemical solar devices, currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic device. DSSCs are based upon the sensitization of mesoporous nanocrystalline metal oxide films to visible light by the adsorption of molecular dyes.5"7 Photoinduced electron injection from the sensitizer dye (D) into the metal oxide conduction band initiates charge separation. Subsequently, the injected electrons are transported through the metal oxide film to a transparent electrode, while a redox-active electrolyte, such as I /I , is employed to reduce the dye cation and transport the resulting positive charge to a counter electrode (Fig. 17.4). 

The effect of passivating films on aluminium and magnesium has been the subject of much research. By incorporating chromate/dichromate mixtures and other substances in the electrolyte, a coherent insoluble oxide film is formed which effectively inhibits further corrosion. Sealed cells with aluminium or magnesium anodes may therefore be successfully stored for several years, even at high temperatures. However, once current has been drawn from the cell, the film is broken down and rapid attack on the metal follows due to reactions such as... 

The accuracy of these measurements of film thickness is subject to some uncertainty, as discussed in the original publication, but for purposes of determining the relationship between the oxide film and the catalytic properties of the surface, the thicknesses given should be significant. 

The rapid development of solid state physics and technology during the last fifteen years has resulted in intensive studies of the application of plasma to thin film preparation and crystal growth The subjects included the use of the well known sputtering technique, chemical vapour deposition ( CVD ) of the solid in the plasma, as well as the direct oxidation and nitridation of solid surfaces by the plasma. The latter process, called plasma anodization 10, has found application in the preparation of thin oxide films of metals and semiconductors. One interesting use of this technique is the fabrication of complementary MOS devices11. Thin films of oxides, nitrides and organic polymers can also be prepared by plasma CVD. 

It has been shown that changes in the UV and IR absorbance of unplasticized Cellophane films subjected to accelerated aging in a dry oven at 140 °C follow the behavior predicted by a first-order kinetic model, except for deviations in the early aging period, and that these deviations are most likely caused by oxidation products in the films. It has also been shown that, for Cellophane films, the changes in UV and IR absorbance follow the same kinetics as color change, and that these kinetics are nearly identical with those for rayon and cotton cloths aged under similar conditions. 

In most corrosion processes passivity is desirable because the rate of electrode dissolution is significantly reduced. The rate of aluminum corrosion in fresh water is relatively low because of the adherent oxide film that forms on the metal surface. A thicker film can be formed on the surface by subjecting it to an anodic current in a process known as anodizing. In most electrochemical conversion processes passive films reduce the reaction rate and are, therefore, undesirable. 

The activation of aluminum with ultrasound or dispersion of liquid aluminum. The suspension of powder aluminum in petrol or n-geptane without oxygen is subjected to ultrasound the tough oxide film on the surface of aluminum is removed and aluminum becomes reactive. The second activation technique is the dispersion of liquid aluminum with argon or purified nitrogen flow into a finely dispersed state. It should be noted, however, that the most reactive aluminum powder for direct synthesis is the powder alloyed with transition metals (titanium, zirconium, niobium, tantalum) with the size of particles from 10 to 125 pm. 

Contrary to the increase in oxidation observed during standard RIE, films subjected to one of the passivation pretreatments (with the exception of the barrel reactor process) showed little further increase in oxide conversion beyond the initial pretreatment conversion. Only the films pretreated by high pressure oxygen plasma in the barrel reactor showed a further increase in oxide conversion on subsequent "standard" RIE (curve 5e). 

Stainless steels offer useful resistance because they tend to exhibit passive corrosion behavior as a result of the formation of protective oxide films on the exposed surfaces. Under normal circumstances, stainless steels will readily form this protective layer immediately on exposure to oxygen. When this protective film is violated or fails to form, active corrosion can occur. Some fabrication processes can impede the reformation of this passive layer, and to insure that it is formed, stainless steels are subjected to passivation treatments. 

---