Atmospheric corrosion oxide film

Application of the primer coat to freshly prepared metal must be as quick as possible to prevent atmospheric agents causing corrosion. Oxide films (corrosion) are not usually securely adhered to the surface of the parent metal and thus can be easily pulled away. If the bonding primer has adhered to the corrosion layer it too will be pulled away from the desired contact between the primer and metal. This corrosion may not be visible to the naked eye, but can result in nnderbond corrosion continuing after vulcanisation. Obviously ambient conditions in the metal preparation area dictate the timing and speed of primer application. 

Aluminum and aluminum alloys are employed in many appHcations because of the abiHty to resist corrosion. Corrosion resistance is attributable to the tightly adherent, protective oxide film present on the surface of the products. This film is 5 —10 nm thick when formed in air if dismpted it begins to form immediately in most environments. The weathering characteristics of several common aluminum alloy sheet products used for architectural appHcations are shown in Eigure 30. The loss in strength as a result of atmospheric weathering and corrosion is small, and the rate decreases with time. The amount of... 

Atmospheric corrosion is electrochemical ia nature and depends on the flow of current between anodic and cathodic areas. The resulting attack is generally localized to particular features of the metallurgical stmcture. Features that contribute to differences ia potential iaclude the iatermetaUic particles and the electrode potentials of the matrix. The electrode potentials of some soHd solutions and iatermetaUic particles are shown ia Table 26. Iron and sUicon impurities ia commercially pure aluminum form iatermetaUic coastitueat particles that are cathodic to alumiaum. Because the oxide film over these coastitueats may be weak, they can promote electrochemical attack of the surrounding aluminum matrix. The superior resistance to corrosion of high purity aluminum is attributed to the small number of these constituents. 

Alloys having varying degrees of corrosion resistance have been developed in response to various environmental needs. At the lower end of the alloying scale are the low alloy steels. These are kon-base alloys containing from 0.5—3.0 wt % Ni, Cr, Mo, or Cu and controlled amounts of P, N, and S. The exact composition varies with the manufacturer. The corrosion resistance of the alloy is based on the protective nature of the surface film, which in turn is based on the physical and chemical properties of the oxide film. As a rule, this alloying reduces the rate of corrosion by 50% over the fkst few years of atmosphere exposure. Low alloy steels have been used outdoors with protection. 

How does galvanising work As Fig. 24.4 shows, the galvanising process leaves a thin layer of zinc on the surface of the steel. This acts as a barrier between the steel and the atmosphere and although the driving voltage for the corrosion of zinc is greater than that for steel (see Fig. 23.3) in fact zinc corrodes quite slowly in a normal urban atmosphere because of the barrier effect of its oxide film. The loss in thickness is typically 0.1 mm in 20 years. 

In the massive state none of these elements is particularly reactive and they are indeed very resistant to atmospheric corrosion at normal temperatures. However, nickel tarnishes when heated in air and is actually pyrophoric if very finely divided (finely divided Ni catalysts should therefore be handled with care). Palladium will also form a film of oxide if heated in air. 

Aluminium is a very reactive metal with a high affinity for oxygen. The metal is nevertheless highly resistant to most atmospheres and to a great variety of chemical agents. This resistance is due to the inert and protective character of the aluminium oxide film which forms on the metal surface (Section 1.5). In most environments, therefore, the rate of corrosion of aluminium decreases rapidly with time. In only a few cases, e.g. in caustic soda, does the corrosion rate approximate to the linear. A corrosion rate increasing with time is rarely encountered with aluminium, except in aqueous solutions at high temperatures and pressures. 

Tantalum is severely attacked at ambient temperatures and up to about 100°C in aqueous atmospheric environments in the presence of fluorine and hydrofluoric acids. Flourine, hydrofluoric acid and fluoride salt solutions represent typical aggressive environments in which tantalum corrodes at ambient temperatures. Under exposure to these environments the protective TajOj oxide film is attacked and the metal is transformed from a passive to an active state. The corrosion mechanism of tantalum in these environments is mainly based on dissolution reactions to give fluoro complexes. The composition depends markedly on the conditions. The existence of oxidizing agents such as sulphur trioxide or peroxides in aqueous fluoride environments enhance the corrosion rate of tantalum owing to rapid formation of oxofluoro complexes. 

The terms hot corrosion or dry corrosion are normally taken to apply to the reactions taking place between metals and gases at temperatures above 100 C i.e. temperatures at which the presence of liquid water is unusual. The obvious cases of wet corrosion at temperatures above 100 C, i.e. in pressurised boilers or autoclaves, are not considered here. In practice, of course, common metals and alloys used at temperatures above normal do not suffer appreciable attack in the atmosphere until the temperature is considerably above 100 C. Thus iron and low-alloy steels form only the thinnest of interference oxide films at about 200 C, copper shows the first evidence of tarnishing at about 180 C, and while aluminium forms a thin oxide film at room temperature, the rate of growth is extremely slow even near the melting point. 

There are many grades of stainless steel, and some are virtually non-corrodible under ordinary atmospheric conditions. Their resistance results from the protective and normally self-repairing oxide film formed on the surface. However, under reducing conditions, or under conditions that prevent the access of oxygen, this film is not repaired, with consequent corrosion. 

The presence of water does not only create conditions for the existence of an electrolyte, but it acts as a solvent for the dissolution of contaminants [10], Oxygen plays an important role as oxidant element in the atmospheric corrosion process. The thickness of the water layer determines the oxygen diffusion toward the metallic surface and also the diffusion of the reaction products to the outside interface limited by the atmosphere. Another aspect of ISO definition is that a metallic surface is covered by adsorptive and/or liquid films of electrolyte . According to new results, the presence of adsorptive or liquid films of electrolyte perhaps could be not in the entire metallic surface, but in places where there is formed a central anodic drop due to the existence of hygroscopic particles or substances surrounded by microdrops where the cathodic process takes place. This phenomenon is particularly possible in indoor conditions [15-18],... 

If one part of a metallic object is protected from the atmosphere so that there is insufficient O2 to build or maintain the oxide film, this protected region will often be the site at which corrosion is most active. The fact that such sites are usually hidden from view accounts for much of the difficulty in detecting and controlling corrosion. 

Aluminum is an active metal and its resistance to corrosion depends on the formation of the protective oxide film. According to the Pourbaix diagram the metal is passive in the pH range —4-9. The protective oxide film formed in water and atmospheres at ambient temperatures is amorphous and a few nanometres in thickness. The stability of the oxide film and its disruption results in corrosion. 

It is well known that SO anions stimulate corrosion of steel surfaces by preventing an in situ formation of iron oxides, which may impede the diffusion processes involved in the corrosion reactions. These sulfate anions are either formed in the atmosphere by oxidation of SO or by direct reaction with the steel surface in the presence of water to form so-called sulfate nests. The latter transformation may take place at the unprotected metal surface or possibly, at least in principal, after SO2 has permeated the organic film and arrived at the metal support. The diffusion of SO anions through organic coatings seems... 

Let us consider the corrosion of metals due to acid rains. Iron and steel structures are highly susceptible to corrosion, and their protection with paint costs billions of US annually. The chemistry of corrosion under atmospheric conditions is extremely complex and is catalyzed by hydrogen ions. This explains why acid deposition causes increased rates of corrosion. Unlike the tightly held oxide film that is formed on aluminum, protecting the metal underneath, iron oxide (rush) provides no such protection to iron and steel. Impurity sites in iron act as cathodes for the reduction of oxygen and the iron acts as the anode... 

Although it readily combines with oxygen, aluminium is resistant to atmospheric corrosion because a thin film of closely adherent oxide is formed which protects the underlying metal from attack. Aluminium powder is therefore used as a pigment in anticorrosive paints. 

CHEMICAL PROPERTIES high thermal neutron cross section resists atmospheric corrosion because of oxide film not attacked by cold mineral acids except hydrogen fluoride not attacked by alkalies evaporation at 20°C is negligible reacts vigorously with strong oxidizers and chlorine FP (NA) LFL/UFL (NA) AT (NA). 

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