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Passivity, although difficult to define, can be quantitatively described by characterizing the behavior of metals that show this unusual effect. first consider the behavior of what can be called an active metal that is a metal that does not show passivity effects. The lower part of the curve in Fig. I illustrates the behavior of such a metal. Assume that a metal is immersed in an air-free acid solution with an oxidizing power corresponding to 6,int a and a corrosion rate corresponding to this point. If the oxidizing power of this solution is increased, say, by adding oxygen or ferric ions, the corrosion rate of the metal will increase rapidly. Note that for such a metal the corrosion rate increases as the oxidizing power of the solution increases. This increase in rate is exponential and yields a straight line when plotted on a semilogarithmic scale as in Fig. 1. The oxidizing power of the solution is controlled by both the specific oxidizing power of the reagents and the concentration of these reagents. Oxidizing power can be precisely defined by electrode potential, but is beyond the scope of this discussion Transpassive 6asN8oco60 Passive Active 100010.000 Corrosion rate Fig. 1 Corrosion characteristics of an active-passive metal as a function of solution oxidizing power(electrode potential) The behavior of this metal or alloy can be conveniently divided into three regions: active, passive, and transpassive. In the active region, slight increases in the oxidizing power of the solution cause a corresponding rapid increase in the corrosion rate. However, at some point, if more oxidizing agent is added the corrosion rate shows a sudden decrease. This corresponds to the beginning of the passive region. Further increases in oxidizing agents produce little if any change in the corrosion rate of the material in the passive region. Finally at very high concentrations of oxidizers or in the presence of very powerful oxidizers, the corrosion rate again increases with increasing oxidizing power. This region is termed the transpassive region It is important to note that during the transition from the active to the passive region, a 10 to 10 reduction in corrosion rate is usually observed. Passivity is due to the formation of a surface film or protective barrier that is stable over a considerable range of oxidizing power and is eventually destroyed in strong oxidizing solutions Under conditions in which the surface film is stable. the anodic reaction is stifled and the metal surface is protected from corrosion. For example, stainless steel owes its corrosion-resistant properties to a passive surface film. The naturally occurring passive film is usually enhanced with immersion in a hot nitric acid solution or steam. For example, stainless steel surgical implants develop this passive layer when the implants are sterilized in steam The exact nature of this barrier that forms on the metal surface is not well understood. It nay be a very thin, transparent oxide film or a layer of adsorbed oxygen atoms. However, for the purposes of engineering application, it is not necessary to understand completely the mechanism. To summarize, metals that possess an active-passive transition become passive(very corrosion-resistant) in moderately to strongly oxidizing environments. Under extremely strong oxidizing conditions, these materials lose their corrosion- resistant properties Thefileisdownloadedfromwww.bzfxw.comPassivity, although difficult to define, can be quantitatively described by characterizing the behavior of metals that show this unusual effect. First, consider the behavior of what can be called an active metal, that is, a metal that does not show passivity effects. The lower part of the curve in Fig. 1 illustrates the behavior of such a metal. Assume that a metal is immersed in an air-free acid solution with an oxidizing power corresponding to point A and a corrosion rate corresponding to this point. If the oxidizing power of this solution is increased, say, by adding oxygen or ferric ions, the corrosion rate of the metal will increase rapidly. Note that for such a metal, the corrosion rate increases as the oxidizing power of the solution increases. This increase in rate is exponential and yields a straight line when plotted on a semilogarithmic scale as in Fig. 1. The oxidizing power of the solution is controlled by both the specific oxidizing power of the reagents and the concentration of these reagents. Oxidizing power can be precisely defined by electrode potential, but is beyond the scope of this discussion. Fig. 1 Corrosion characteristics of an active-passive metal as a function of solution oxidizing power (electrode potential) The behavior of this metal or alloy can be conveniently divided into three regions: active, passive, and transpassive. In the active region, slight increases in the oxidizing power of the solution cause a corresponding rapid increase in the corrosion rate. However, at some point, if more oxidizing agent is added, the corrosion rate shows a sudden decrease. This corresponds to the beginning of the passive region. Further increases in oxidizing agents produce little if any change in the corrosion rate of the material in the passive region. Finally, at very high concentrations of oxidizers or in the presence of very powerful oxidizers, the corrosion rate again increases with increasing oxidizing power. This region is termed the transpassive region. It is important to note that during the transition from the active to the passive region, a 103 to 106 reduction in corrosion rate is usually observed. Passivity is due to the formation of a surface film or protective barrier that is stable over a considerable range of oxidizing power and is eventually destroyed in strong oxidizing solutions. Under conditions in which the surface film is stable, the anodic reaction is stifled and the metal surface is protected from corrosion. For example, stainless steel owes its corrosion-resistant properties to a passive surface film. The naturally occurring passive film is usually enhanced with immersion in a hot nitric acid solution or steam. For example, stainless steel surgical implants develop this passive layer when the implants are sterilized in steam. The exact nature of this barrier that forms on the metal surface is not well understood. It may be a very thin, transparent oxide film or a layer of adsorbed oxygen atoms. However, for the purposes of engineering application, it is not necessary to understand completely the mechanism. To summarize, metals that possess an active-passive transition become passive (very corrosion-resistant) in moderately to strongly oxidizing environments. Under extremely strong oxidizing conditions, these materials lose their corrosion￾resistant properties. The file is downloaded from www.bzfxw.com
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