Anodic inhibitors

Cathodic inhibitors Anodic inhibitors Mixed type inhibitors... 

The effect of addition of mixed inhibitors (anodic and cathodic both) is shown in Fig. 6.9. Mixed inhibitors show the characteristics of both the types of inhibitors seen in Figs 6.8a and b. 

It is very rare that a single inhibitor is used in systems such as cooling water systems. More often, a combination of inhibitors (anodic and cathodic) is used to obtain better corrosion protection properties. The blends which are produced by mbdng of multi-inhibitors are called synergistic blends. Examples include chromate-phosphates, polyphosphate-silicate, zinc-tannins, zinc-phosphates. Phosphonates have been used to cathodically protect ferrous materials. Following are the major applications of synergistic blends of inhibitors. 

Crevice Corrosion. Crevice corrosion is intense locali2ed corrosion that occurs within a crevice or any area that is shielded from the bulk environment. Solutions within a crevice are similar to solutions within a pit in that they are highly concentrated and acidic. Because the mechanisms of corrosion in the two processes are virtually identical, conditions that promote pitting also promote crevice corrosion. Alloys that depend on oxide films for protection (eg, stainless steel and aluminum) are highly susceptible to crevice attack because the films are destroyed by high chloride ion concentrations and low pH. This is also tme of protective films induced by anodic inhibitors. 

Passivating (anodic) inhibitors form a protective oxide film on the metal surface they are the best inhibitors because they can be used in economical concentrations and their protective films are tenacious and tend to be rapidly repaired if damaged. 

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. 

Copper Corrosion Inhibitors. The most effective corrosion inhibitors for copper and its alloys are the aromatic triazoles, such as benzotriazole (BZT) and tolyltriazole (TTA). These compounds bond direcdy with cuprous oxide (CU2O) at the metal surface, forming a "chemisorbed" film. The plane of the triazole Hes parallel to the metal surface, thus each molecule covers a relatively large surface area. The exact mechanism of inhibition is unknown. Various studies indicate anodic inhibition, cathodic inhibition, or a combination of the two. Other studies indicate the formation of an insulating layer between the water surface and the metal surface. A recent study supports the idea of an electronic stabilization mechanism. The protective cuprous oxide layer is prevented from oxidizing to the nonprotective cupric oxide. This is an anodic mechanism. However, the triazole film exhibits some cathodic properties as well. 

Inhibitors act and are classified in a variety of ways (1,3,37,38). The classifications used herein closely foUow the discussion in Reference 37. Types of inhibitors include (/) anodic, (2) cathodic, (3) organic, (4) precipitation, and (5) vapor-phase inhibitors. 

Anodic Inhibitors. Passivating or anodic inhibitors produce a large positive shift in the corrosion potential of a metal. There are two classes of anodic inhibitors which are used for metals and alloys where the anodic shift in potential promotes passivation, ie, anodic protection. The fkst class includes oxidking anions that can passivate a metal in the absence of oxygen. Chromate is a classical example of an oxidking anodic inhibitor for the passivation of steels. 

The second class of anodic inhibitors contains ions which need oxygen to passivate a metal. Tungstate and molybdate, for example, requke the presence of oxygen to passivate a steel. The concentration of the anodic inhibitor is critical for corrosion protection. Insufficient concentrations can lead to pitting corrosion or an increase in the corrosion rate. The use of anodic inhibitors is more difficult at higher salt concentrations, higher temperatures, lower pH values, and in some cases, at lower oxygen concentrations (37). 

Inhibitors The use of various substances or inhibitors as additives to corrosive environments to decrease corrosion of metals in the environment is an important means of combating corrosion. This is generally most attractive in closed or recirculating systems in which the annual cost of inhibitor is low. However, it has also proved to be economicaUv attrac tive for many once-through systems, such as those encountered in petroleum-processing operations. Inhibitors are effective as the result of their controlling influence on the cathode- or anode-area reactions. 

Sample pre-treatment. Novel procedures of electrochemical sample treatment have been proposed to decrease the signal interference with native cholinesterase inhibitors present in fruits and vegetables. Polyphenolic compounds were removed by electrolysis with soluble A1 anode followed by the oxidation of thionic pesticides with electrogenerated chlorine. The procedure proposed makes it possible to decrease the background current and the matrix effect by 80-90%. Thus, the detection limits of about 5 ppb of Pai athion-Methyl and Chloropyrifos-Methyl were obtained in spiked grape juice without any additional sepai ation or pre-concentration stages. 

Chemical inhibitors, when added in small amounts, reduce corrosion by affecting cathodic and/or anodic processes. A wide variety of treatments may be used, including soluble hydroxides, chromates, phosphates, silicates, carbonates, zinc salts, molybdates, nitrates, and magnesium salts. The exact amount of inhibitor to be used, once again, depends on system parameters such as temperature, flow, water chemistry, and metal composition. For these reasons, experts in water treatment acknowledge that treatment should be fine tuned for a given system. 

Besides the use of anodic polarization with impressed current to achieve passivation, raising the cathodic partial current density by special alloying elements and the use of oxidizing inhibitors (and/or passivators) to assist the formation of passive films can be included in the anodic protection method [1-3]. 

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. 

Inhibitors are materials that reduce either one or both of the partial corrosion reactions as in Fig. 2-5. Anodic or cathodic inhibitors inhibit the anodic or cathodic reaction respectively so that the rest potential becomes either more positive or more negative. Most inhibitors, however, inhibit the anodic partial reaction. This is because the transfer of metal ions can be more easily restricted than that of electrons. 

Anodic Inhibitor-a chemical constituent that reduces the rate of anodic or oxidation reaction. 

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

Hatch, G. B., Maximum Self-generated Anodic Current Density as an Inhibitor Pitting Index , III. State Water Surv., Circ. No. 91, 24 (1966) C.A., 66, 8l8l4f Herbsleb, G., Pitting Corrosion on Metals with Elearon-conductive Passive Layers , tVerksl. Korros., 17, 649 (1966) C.A., 66, 5337m ... 

The use of soluble inhibitors as a means of controlling bimetallic corrosion presents many technical problems. Apart from the fact that this method is limited in applicability to recirculating systems, efficient anodic inhibitors, such as chromates, are frequently quite specific in their action and so certain bimetallic couples, such as the Al-Cu couple in chloride solutions, are... 

It has been shown that pure distilled water is least corrosive when fully aerated and that some inhibitors function better in the presence of oxygen In these cases oxygen acts as a passivator of the anodic areas of the corrosion cells. These facts do not, however, modify the foregoing statements on the significance of oxygen in waters as used in practice. 

Some salts, notably chromates, dichromates, silicates, borates and cinna-mates, have marked inhibitive power and are very effective in closed-circuit water systems. Care must be taken to ensure that a sufficient quantity of such anodic inhibitors as chromates is added, as otherwise attack, though occurring at fewer points, may be more severe at these points. Chromates and dichromates have little inhibitive power in strongly acid solutions. 

As with most other metals, the anodic behaviour of nickel is influenced by the composition of the solution in which measurements are made, particularly if the solution is acidic. Acidic solutions containing d ions or certain sulphur compounds in particular have a pronounced influence both in increasing the rate of anodic dissolution in the active range and in preventing passivation, and in stimulating localised corrosion . Thiourea and some of its derivatives have a complex effect, acting either as anodic stimulators or inhibitors, depending on their concentration . 

Conversely to the above, any factor which tends to maintain the protective character of the beryllia film will obviously increase corrosion resistance, and, in this respect, the presence of anodic inhibitors such as sodium dichromate, up to about 40 p.p.m., will effectively suppress pitting of beryllium in water. 

---