Oxide films alloying effects

Copper and Copper-Containing Alloys. Either sulfuric or hydrochloric acid may be used effectively to remove the oxide film on copper (qv) or copper-containing alloys. Mixtures of chromic and sulfuric acids not only remove oxides, but also brighten the metal surface. However, health and safety issues related to chromium(VT) make chromic acid less than desirable. 

Chromium is an essential constituent in alloys to be used above 550°C (1,000°F). It provides a tightly adherent oxide film that materially retards the oxidation process. Sihcon is a usebil element in imparting oxidation resistance to steel. It will enhance the beneficial effects of chromium. Also, for a given level of chromium, experience has shown oxidation resistance to improve as the nickel content increases. 

The high-chromium irons undoubtedly owe their corrosion-resistant properties to the development on the surface of the alloys of an impervious and highly tenacious film, probably consisting of a complex mixture of chromium and iron oxides. Since the chromium oxide will be derived from the chromium present in the matrix and not from that combined with the carbide, it follows that a stainless iron will be produced only when an adequate excess (probably not less than 12% of chromium over the amount required to form carbides is present. It is commonly held, and with some theoretical backing, that carbon combines with ten times its own weight of chromium to produce carbides. It has been said that an increase in the silicon content increases the corrosion resistance of the iron this result is probably achieved because the silicon refines the carbides and so aids the development of a more continuous oxide film over the metal surface. It seems likely that the addition of molybdenum has a similar effect, although it is possible that the molybdenum displaces some chromium from combination with the carbon and therefore increases the chromium content of the ferrite. 

Contact with steel, though less harmful, may accelerate attack on aluminium, but in some natural waters and other special cases aluminium can be protected at the expense of ferrous materials. Stainless steels may increase attack on aluminium, notably in sea-water or marine atmospheres, but the high electrical resistance of the two surface oxide films minimises bimetallic effects in less aggressive environments. Titanium appears to behave in a similar manner to steel. Aluminium-zinc alloys are used as sacrificial anodes for steel structures, usually with trace additions of tin, indium or mercury to enhance dissolution characteristics and render the operating potential more electronegative. 

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. 

Compared with ferritic carbon and low-alloy steels, relatively little information is available in the literature concerning stainless steels or nickel-base alloys. From the preceding section concerning low-alloy steels in high temperature aqueous environments, where environmental effects depend critically on water chemistry and dissolution and repassivation kinetics when protective oxide films are ruptured, it can be anticipated that this factor would be of even more importance for more highly alloyed corrosion-resistant materials. 

Although aluminium is a base metal, it spontaneously forms a highly protective oxide film in most aqueous environments, i.e. it passivates. In consequence, it has a relatively noble corrosion potential and is then unable to act as an anode to steel. Low level mercury, indium or tin additions have been shown to be effective in lowering (i.e. making more negative) the potential of the aluminium they act as activators (depassivators). Each element has been shown to be more effective with the simultaneous addition of zinc . Zinc additions of up to 5% lower the anode operating potential, but above this level no benefit is gained . Below 0 9 7o zinc there is little influence on the performance of aluminium anodes . Table 10.10 lists a number of the more common commercial alloys. 

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. 

In most Al-containing alloys, the shape of the particles was tear-drop like due to the tight surface oxide film. The typical shape was shown in Fig.l. The effect of rapid solidification on microstructures is shown in Fig. 5 for AI2CU (precursor for Raney Cu) with a small amount of Pd (11). In the case of slowly solidified (conventional) precursor, most of the added Pd was solidified as a secondary Pd rich phase shown by white dendritic structure in Fig.5 (a). On the other hand, no such secondary phase was observed in a rapidly solidified precursor as shown in Fig.5 (b). 

In the past ten years the number of chemistry-related research problems in the nuclear industry has increased dramatically. Many of these are related to surface or interfacial chemistry. Some applications are reviewed in the areas of waste management, activity transport in coolants, fuel fabrication, component development, reactor safety studies, and fuel reprocessing. Three recent studies in surface analysis are discussed in further detail in this paper. The first concerns the initial corrosion mechanisms of borosilicate glass used in high level waste encapsulation. The second deals with the effects of residual chloride contamination on nuclear reactor contaminants. Finally, some surface studies of the high temperature oxidation of Alloys 600 and 800 are outlined such characterizations are part of the effort to develop more protective surface films for nuclear reactor applications. ... 

The corrosion resistance of steel can be greatly increased by alloying with chromium to form the stainless steels. Figure 12 shows the effect of increasing chromium content on the corrosion rate of steel. At 12-14% Cr there is a dramatic decrease in corrosion rate. The corrosion resistance is due to the formation of a thin adherent layer of chromium oxide on the steel surface [23]. The steel will remain stainless provided the oxide layer remains intact or can be rapidly repaired, i.e. the steel is exposed to oxidising conditions. The precipitation of chromium carbide at grain boundaries will cause disruption of this oxide film (See Sect. 3.2.5) and hence localised corrosion. Precipitation of chromium carbide can be reduced by alloying with elements which form carbides more readily than chromium, e.g. titanium, niobium, and tantalum. 

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