Anodic passivating inhibitors

There are basically three main types of inorganic inhibitors used in industry anodic passivating inhibitors, cathodic inhibitors and cathodic precipitators. 

Precipita.tingInhibitors. As discussed earlier, the localized pH at the cathode of the corrosion cell is elevated due to the generation of hydroxide ions. Precipitating inhibitors form complexes that are insoluble at this high pH (1—2 pH units above bulk water), but whose deposition can be controlled at the bulk water pH (typically 7—9 pH). A good example is zinc, which can precipitate as hydroxide, carbonate, or phosphate. Calcium carbonate and calcium orthophosphate are also precipitating inhibitors. Orthophosphate thus exhibits a dual mechanism, acting as both an anodic passivator and a cathodic precipitator. 

Three types of anodic protection can be distinguished (1) impressed current, (2) formation of local cathodes on the material surface and (3) application of passivating inhibitors. For impressed current methods, the protection potential ranges must be determined by experiment (see information in Section 2.3). Anodic protection with impressed current has many applications. It fails if there is restricted current access (e.g., in wet gas spaces) with a lack of electrolyte and/or in the... 

Passivating inhibitors act in two ways. First they can reduce the passivating current density by encouraging passive film formation, and second they raise the cathodic partial current density by their reduction. Inhibitors can have either both or only one of these properties. Passivating inhibitors belong to the group of so-called dangerous inhibitors because with incomplete inhibition, severe local active corrosion occurs. In this case, passivated cathodic surfaces are close to noninhibited anodic surfaces. 

Anodically colored electrochromic inorganic films, 6 579-580 Anodic cleaning, 9 783, 785 Anodic (passivating) corrosion inhibitors, 26 144... 

It is important not to leave the system empty of water for any long period, as rapid surface rusting will take place. As soon as the closed-loop system is declared free of contamination, sufficient corrosion inhibitor is added to provide long-term corrosion protection. The corrosion inhibitor is usually an anodic, passivating formulation, typically based on nitrite or tannin (and often in combination with phosphate, silicate, borate, or molybdate, etc.). Finally, after confirmation that the entire system is adequately treated (which usually requires the inhibited water in the system to be recirculated for a further 16 to 24 hours), the system is signed off and handed over. 

Some inhibitors produce films on the anode and hence stifle the corrosion reaction (iron in chromate or nitrite solutions). Several authors consider the presence of a thick barrier of corrosion products, relatively protective, on the metallic surface as passivation. Inhibitors may enhance the formation of passive films on top of the substrate, such as benzotriazole on copper or benzoate on iron, or they may form monomolecular... 

Passivation Inhibitors. Examples of passivators (anodic inhibitors) include chromate, nitrite, molybdate, and orthophosphate. AH are oxidizers and promote passivation by increasing the electrical potential of the iron. Chromate and nitrite do not require oxygen, and thus, can he the most effective. Chromate is an excellent aqueous corrosion inhibitor, particularly from a cost perspective. However, owing to health and environmental concerns, use of chromate has decreased significandy and will probably he outlawed soon. Nitrite is also an effective inhibitor, but in open systems it tends to be oxidized to nitrate. 

Anodic passivation of steel surfaces can be efficiently achieved by metal chromates. Chromates of Intermediate solubility (e.g., zinc chromate and strontium chromate) allow a compromise between mobility in the film and leaching from the film to be achieved. Chromates inhibit corrosion in aqueous systems by formation of a passivating oxide film. The effectiveness of chromate inhibitors in aqueous systems depends on the concentration of other ionic species in solution, for example, chloride. Synthetic resin composition can also significantly influence the effectiveness of chromate pigments. The effect appears to be related to the polarity of the resin (20) chromate pigments appear to be less effective in resins of low polarity. 

Anodic inhibitors increase anode polarization to the critical passivation potential of the metal or alloy. They are called passivating inhibitors because they drastically decrease the corrosion current. Figure 14.2a and b illustrate the polarization and passivation effect of anodic inhibitors. These inhibitors are strong oxidizing agents and shift the corrosion potential of the metal in the noble direction with the formation of a passive film. 

Fig. 14.2 (a) Polarization diagram illustrating the polarization effect of an anodic inhibitor and (b) polarization diagram illustrating the effect of an anodic passivation. 

Non-passivating inhibitors include both some anodic (Figure 10.5c) and the cathodic ones (Figure 10.5d). The latter are exemplified by those that remove free oxygen by a reaction, as is the case for hydrazine and sodium sulphite ... 

There are two types of passivating inhibitors oxidizing anions such as chromate, nitrite, and nitrate, which can passivate steel in the absence of oxygen, and the nonoxidizing ions such as phosphate, tungstate, and molybdate, which require the presence of oxygen to passivate steel. Examples of passivators (anodic inhibitors) include chromate, nitrite, and orthophosphate (Dihua et al. 1999). 

Inhibitors can also be classified on the basis of their functions. For instance, chromates and nitrates are called passivating inhibitors because of their tendency to passivate the metal surface. Some inhibitors, such as silicates, inhibit both the anodic and cathodic reactions. They also remove undesirable suspended particles from the system, such as iron particles, by precipitation. Certain types of inhibitors make the surrounding environment alkaline to prevent corrosion. Such inhibitors in the gas phase are called vapor phase inhibitors, and they consist of heterocyclic compounds, such as cyclohexylamine. These inhibitors are used within packing crates during transportation by sea. 

Cathodic, anodic or passivating inhibitors are commonly used to prevent corrosion of steel reinforcement. In the class of anodic inhibitors, calcium nitrite, sodium nitrite, sodium benzoate and sodium chromate are commonly used. Cathodic inhibitors mainly consist of amines. 

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