Protective aqueous corrosion

Silicates. For many years, siUcates have been used to inhibit aqueous corrosion, particularly in potable water systems. Probably due to the complexity of siUcate chemistry, their mechanism of inhibition has not yet been firmly estabUshed. They are nonoxidizing and require oxygen to inhibit corrosion, so they are not passivators in the classical sense. Yet they do not form visible precipitates on the metal surface. They appear to inhibit by an adsorption mechanism. It is thought that siUca and iron corrosion products interact. However, recent work indicates that this interaction may not be necessary. SiUcates are slow-acting inhibitors in some cases, 2 or 3 weeks may be required to estabUsh protection fully. It is beheved that the polysiUcate ions or coUoidal siUca are the active species and these are formed slowly from monosilicic acid, which is the predorninant species in water at the pH levels maintained in cooling systems. 

Additionally, crevice corrosion can be reduced by two techniques used successfully on most aqueous corrosion—chemical inhibition and cathodic protection. However, both these techniques may be cost prohibitive. 

The processes of cathodic protection can be scientifically explained far more concisely than many other protective systems. Corrosion of metals in aqueous solutions or in the soil is principally an electrolytic process controlled by an electric tension, i.e., the potential of a metal in an electrolytic solution. According to the laws of electrochemistry, the reaction tendency and the rate of reaction will decrease with reducing potential. Although these relationships have been known for more than a century and although cathodic protection has been practiced in isolated cases for a long time, it required an extended period for its technical application on a wider scale. This may have been because cathodic protection used to appear curious and strange, and the electrical engineering requirements hindered its practical application. The practice of cathodic protection is indeed more complex than its theoretical base. 

In principle, cathodic protection can be applied to all the so-called engineering metals. In practice, it is most commonly used to protect ferrous materials and predominantly carbon steel. It is possible to apply cathodic protection in most aqueous corrosive environments, although its use is largely restricted to natural near-neutral environments (soils, sands and waters, each with air access). Thus, although the general principles outlined here apply to virtually all metals in aqueous environments, it is appropriate that the emphasis, and the illustrations, relate to steel in aerated natural environments. 

Whilst cathodic protection can be used to protect most metals from aqueous corrosion, it is most commonly applied to carbon steel in natural environments (waters, soils and sands). In a cathodic protection system the sacrificial anode must be more electronegative than the structure. There is, therefore, a limited range of suitable materials available to protect carbon steel. The range is further restricted by the fact that the most electronegative metals (Li, Na and K) corrode extremely rapidly in aqueous environments. Thus, only magnesium, aluminium and zinc are viable possibilities. These metals form the basis of the three generic types of sacrificial anode. 

Coatings of tin produced from tin-containing aqueous solutions by chemical replacement may be used to provide special surface properties such as appearance or low friction, but protect from corrosion only in non-aggressive environments. Copper and brass may be tinned in alkaline cyanide solutions or in acid solutions containing organic addition agents such as thiourea. Steel may be first coated with copper and then treated... 

Steel objects are often protected from corrosion by electroplating with chromium. The most straightforward process would be to electrolyze a solution of Cr cations. This fails because aqueous Cr ions are not reduced at a useful rate. Instead, solutions containing chromate anions are used ... 

At the other extreme, the oxide layers on aluminum, beryllium, titanium, vanadium, chromium, nickel, and tantalum are very insoluble in water at intermediate pH values and do not have easily accessible reduced states with higher solubility. The oxide films on those metals are therefore highly protective against aqueous corrosion. 

In general, the susceptibility of metals M to aqueous corrosion is expected to correlate inversely with the E° values for the reduction of Mm+(aq) to M(s) the less positive E° is, the greater is the tendency of M to corrode in aerated water. Factors that can upset predictions based on E° include the presence of protective films (passivation), overpotential effects (Sections 15.4 and 16.6), effects of complexing agents, and incursion of a cathode reaction other than O2 reduction or H2 evolution. 

Aqueous corrosion can occur even when the metallic object to be protected is ostensibly not immersed in water, if the relative humidity of the atmosphere exceeds 60%. In that case, a film of water will in fact be present on the metal surface. Further, if sulfur dioxide is present in the air, corrosion in the thin film of water will be greatly accelerated, partly because the acidity of the dissolved SO2 facilitates the oxygen absorption reaction... 

Chemical passivity corresponds to the state where the metal surface is stable or substantially unchanged in a solution with which it has a thermodynamic tendency to react. The surface of a metal or alloy in aqueous or organic solvent is protected from corrosion by a thin film (1—4 nm), compact, and adherent oxide or oxyhydroxide. The metallic surface is characterized by a low corrosion rate and a more noble potential. Aluminum, magnesium, chromium and stainless steels passivate on exposure to natural or certain corrosive media and are used because of their active-passive behavior. Stainless steels are excellent examples and are widely used because of their stable passive films in numerous natural and industrial media.6... 

Chemical process plants often use epoxy, acrylic, polyurethane, and other coatings to prevent corrosion.107 Food cans often have epoxy resin linings. A coating made by the plasma polymerization of a 1 1 perfluorobutane-hy-drogen mixture protected copper from aqueous corrosion.108 Auto makers often use electrogalvanized steel... 

Already in 1952 the effectiveness of TcOj ions in aqueous solutions for the corrosion inhibition of iron and carbon steels was discovered [32.33]. A specimen of steel was efficiently protected against corrosion at temperatures of up to at least 250 "C in aerated distilled water containing 5-10 M TcOj, one-tenth of the concentration required for corrosion inhibition by CrO. The test specimen remained bright and unchanged in weight after being exposed for 20 years in the aqueous TCO4 solution at pH 6. To achieve inhibition under very corrosive conditions not more than 2.2 lO technetium atoms per cm- must be deposited on the surface of the specimen, about a tenth of a monolayer, ffowever. an inhibited specimen corroded at once when... 

It is well known that quite low concentrations of certain oxygen-containing anions, such as chromate, are effective inhibitors of aqueous corrosion of a number of metals. These results have been ascribed to specific adsorption of the inhibitor at anodic sites of the metal surface, or alternatively to continuous repair of the protective film. 

Corrosion refers to the degradation of a metal by electrochemical reaction with the environment. At room temperature, the most important corrosion reactions involve water, and the process is known as aqueous corrosion. (Corrosion at high temperatures in dry air, called oxidation tarnishing, or direct corrosion, is considered in Section 8.5.) Aqueous corrosion involves a set of complex electrochemical reactions in which the metal reverts to a more stable condition, usually an oxide or mixture of oxides and hydroxides (Figure 9.15). In many cases the products are not crystalline and are frequently mixtures of compounds. Aside from the loss of metal, the corrosion products may be voluminous. In this case, they force overlying protective layers away from the metal and so allow corrosion to proceed unchecked, which exacerbates the damage. 

It is well known that the less porous the polymer, the better is the barrier effect, and the better the metal is protected against corrosion [41,42]. Unfortunately, native conducting polymers prepared by electropolymerization of a monomer in aqueous media and deposited directly onto the metal are very porous [77]. Moreover, polymer synthesis in aqueous media leads to native films containing large amounts of water, which are detrimental [41,42]. In general, the films are dried in air, but, even after that, the water content remains high. Clearly, submitting the material to thermal treatment, in order to remove all the water inside the polymer and make it more compact, should improve the barrier effect. 

An alkyd resin containing less than 1% PANI was examined for its ability to protect carbon steel against aqueous corrosion. In field tests, in urban and marine environments, as well as in accelerated laboratory tests, the presence of PANI in the alkyd resin improved the corrosion protection of carbon steel and also the degradation resistance of the coating [214]. 

J. R. Scully and R. G. Kelly, Methods for Determining Aqueous Corrosion Reaction Rates, in AS M Handbook, Vol. 13A, Corrosion Fundamentals, Testing, and Protection, ASM International, Materials Park, OH, 2003, p. 73. 

The special case of the bimetallic effect between a zinc coating and the substrate that it is protecting is discussed under hot water aqueous corrosion resistance as the normal bimetallic effect whereby zinc protects steel is reversed in some waters, usually at 60-90°C. Bimetallic corrosion of zinc occurs mainly when zinc or zinc-coated steel is protecting uncoated steel or other base metals such as copper. Many of the uses of zinc deliberately invoke this principle, but in other cases an unwanted effect arises as a result of constructional requirements, and avoidance of bimetallic corrosion is needed. 

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