Atmospheres, corrosive

Atmospheric corrosion results from a metal s ambient-temperature reaction, with the earth s atmosphere as the corrosive environment. Atmospheric corrosion is electrochemical in nature, but differs from corrosion in aqueous solutions in that the electrochemical reactions occur under very thin layers of electrolyte on the metal surface. This influences the amount of oxygen present on the metal surface, since diffusion of oxygen from the atmosphere/electrolyte solution interface to the solution/metal interface is rapid. Atmospheric corrosion rates of metals are strongly influenced by moisture, temperature and presence of contaminants (e.g., NaCl, SO2,. ..). Hence, significantly different resistances to atmospheric corrosion are observed depending on the geographical location, whether mral, urban or marine. 

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. 

Atmospheric exposure, fresh and salt waters, and many types of soil can cause uniform corrosion of copper aHoys. The relative ranking of aHoys for resistance to general corrosion depends strongly on environment and is relatively independent of temper. Atmospheric corrosion, the least damaging of the various forms of corrosion, is generaHy predictable from weight loss data obtained from exposure to various environments (31) (see Corrosion and CORROSION CONTKOL). 

Excellent resistance to saltwater corrosion and biofouling are notable attributes of copper and its dilute alloys. High resistance to atmospheric corrosion and stress corrosion cracking, combined with high conductivity, favor use in electrical/electronic appHcations. 

Tin—Nickel. AHoy deposits having 65% fin have been commercially plated siace about 1951 (135). The 65% fin alloy exhibits good resistance to chemical attack, staining, and atmospheric corrosion, especially when plated copper or bron2e undercoats are used. This alloy has a low coefficient of friction. Deposits are solderable, hard (650—710 HV ), act as etch resists, and find use ia pfinted circuit boards, watch parts, and as a substitute for chromium ia some apphcafions. The rose-pink color of 65% fin is attractive. In marine exposure, tin—nickel is about equal to nickel—chromium deposits, but has been found to be superior ia some iadustfial exposure sites. Chromium topcoats iacrease the protection further. Tia-nickel deposits are bfitde and difficult to strip from steel. Temperature of deposits should be kept below 300°C. 

Atmospheric corrosion. Air-cooled heat exchangers should not be located where corrosive vapors and fumes from vent stacks will pass through them. 

It is agreed generally that the characteristics of the rust films that form on steels determine their resistance to atmospheric corrosion. The rust films that form on low-aUoy steels are more protec tive than those that form on unalloyed steel. 

With some important exceptions, gray-iron castings generally have corrosion resistance similar to that of carbon steel. They do resist atmospheric corrosion as well as attack by natural or neutral waters and neutral soils. However, dilute acids and acid-salt solutions will attack this material. 

Mild steel, also low-alloy irons and steels 0 3 0 3 < 400 1 < 750 Wronglit, cast Good Good 67 6.7 Higli strengths obtainable by alloying, also improved atmospheric corrosion resistance. See ASTM specifications for particular grade... 

A frequently cited example of protection from atmospheric corrosion is the Eiffel Tower. The narrow and, for that age, thin sections required a good priming of red lead for protection against corrosion. The top coat was linseed oil with white lead, and later coatings of ochre, iron oxide, and micaceous iron oxide were added. Since its constmction the coating has been renewed several times [29]. Modern atmospheric corrosion protection uses quick-drying nitrocellulose, synthetic resins, and reaction resins (two-component mixes). The chemist Leo Baekeland discovered the synthetic material named after him, Bakelite, in 1907. Three years later the first synthetic resin (phenol formaldehyde) proved itself in a protective paint. A new materials era had dawned. 

Data from H. R. Copson, Report of ASTM Subcommittee VI, of Committee B-3 on Atmospheric Corrosion, Am. Soc. Test Mater., Spec. Tech. Publ. 175, 1955. Used by permission of the American Society for Testing and Materials, Philadelphia. 

The consumption of oxygen due to atmospheric corrosion of sealed metal tanks may cause a hazard, due to oxygen-deficiency affecting persons on entry. 

Critical Humidity—the relative humidity (RH) at and above which the atmospheric corrosion rate of a metal increases significantly. 

Zinc diffusion is used for protection against atmospheric corrosion. Aluminum diffusion is used to improve the oxidation resistance of low-carbon steels. 

BS2569 Sprayed Metal Coatings. Part 1 Protection of Iron and Steel by Aluminum and Zinc Against Atmospheric Corrosion. ... 

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. 

Fin material preferred from atmospheric corrosion standpoint. 

Apply appropriate film-forming inhibitors to reduce atmospheric corrosion during storage and transit. 

Impedance spectroscopy This technique is essentially the extension of polarization resistance measurements into low-conductivity environments, including those listed above. The technique can also be used to monitor atmospheric corrosion, corrosion under thin films of condensed liquid and the breakdown of protective paint coatings. Additionally, the method provides mechanistic data concerning the corrosion processes, which are taking place. 

The classification given in Table 1.2 is based on the various forms that corrosion may take, but the terminology used in describing corrosion phenomena frequently places emphasis on the environment or cause of attack rather than the form of attack. Thus the broad classification of corrosion reactions into wet or dry is now generally accepted, and the nature of the process is frequently made more specific by the use of an adjective that indicates type or environment, e.g. concentration—cell corrosion, crevice corrosion, bimetallic corrosion and atmospheric corrosion. 

The main factor in causing filiform corrosion is the relative humidity of the atmosphere, and if this is below 65% (the critical relative humidity for the atmospheric corrosion of most metals, see Section 2.2) it will not occur. As the relative humidity increases the thickness of the filaments increases at 65-80% relative humidity they are very thin, at 80-95% relative humidity they are much wider and at approximately 95% relative humidity they broaden sufficiehtly to form blisters. 

There are many special factors controlling atmospheric bimetallic corrosion that entitle it to separate treatment. The electrolyte in atmospheric corrosion consists of a thin condensed film of moisture containing any soluble contaminants in the atmosphere such as acid fumes from industrial atmospheres and chlorides from marine atmospheres. This type of electrolyte has two characteristics which are summarised in a paper by Rosenfel d . 

Kucera, V. and Mattson, E., Atmospheric Corrosion of Bimetallic Structures, ex Atmospheric Corrosion, 561, J. Wiley and Sons, (1982)... 

The above work is important, since many practical corrosion systems involve a thick but porous film of corrosion products, e.g. rusting, sul-phatising, tuberculation and atmospheric corrosion, and the approach may lead to a more valid corrosion testing technique for these situations. 

Metals are more frequently exposed to the atmosphere than to any other corrosive environment. Atmospheric corrosion is also the oldest corrosion problem known to mankind, yet even today it is not fully understood. The principal reason for this paradox lies in the complexity of the variables which determine the kinetics of the corrosion reactions. Thus, corrosion rates vary from place to place, from hour to hour and from season to season. Equally important, this complexity makes meaningful results from laboratory experiments very difficult to obtain. 

However, the object of this section is to outline the principles which govern atmospheric corrosion, and the emphasis is placed on metals whose atmospheric corrosion is of economic importance. These include iron and steel, zinc, copper, lead, aluminium and chromium. 

However, in this section emphasis is placed upon damp and wet atmospheric corrosion which are characterised by the presence of a thin, invisible film of electrolyte solution on the metal surface (damp type) or by visible deposits of dew, rain, sea-spray, etc. (wet type). In these categories may be placed the rusting of iron and steel (both types involved), white rusting of zinc (wet type) and the formation of patinae on copper and its alloys (both types). 

The composition given in Table 2.8 is global and, for most components, is reasonably constant for all locations, but the water vapour content will obviously vary according to the climatic region, season of the year, time of the day, etc. However, only oxygen, carbon dioxide and water vapour need to be considered in the context of atmospheric corrosion. 

Sulphur oxides These (SO2 is the most frequently encountered oxide) are powerful stimulators of atmospheric corrosion, and for steel and particularly zinc the correlation between the level of SO2 pollution and corrosion rates is good However, in severe marine environments, notably in the case of zinc, the chloride contamination may have a higher correlation coefficient than SO2. 

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