Atmospheric corrosion surface

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. 

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). 

Table 3.4 Effect of the surface condition at the time of exposure on the atmospheric corrosion of mild steel (BISRA) (5 years outdoor exposure at Sheffield)...

The atmospheric corrosion data in Table 4.34 (and also Table 13.8) is related to historic environments. Current use in the industrial areas listed with acidic pollution would show much lower corrosion rates as the corrosion of zinc in the atmosphere is essentially related to the SOj content (and the time of wetness) and in many countries the sulphurous pollution has been greatly reduced in the past 20 years. Zinc also benefits from rainwater washing to remove corrosive poultices thus, although initial corrosion rates are usually not very different on upper and lower surfaces, the latter tend —with time—to become encrusted with corrosion products and deposits and these are not always protective. 

There are also occasions, particularly in hydrogen-containing atmospheres, when surface contamination of the titanium with iron can result in localised corrosion and embrittlement. This effect can be countered by avoidance of undue contamination with iron during fabrication, by postfabrication cleaning and by post-fabrication anodisingIt should be emphasized, however, that in general use in the marine and chemical industries discussed below, iron levels up to 0-2% do not adversely affect corrosion resistance. 

The reason for the use of zinc as a power-impressed rather than a sacrificial anode is that the high concrete resistivity limits the current output, and a higher driving voltage than that provided by the e.m.f. between zinc and steel in concrete is used to provide the necessary current output. No cementitious overlay is required, although it may be advisable to paint the top surface of the sprayed zinc to prevent atmospheric corrosion of the zinc anode. 

Fig. 12.9 Corrosion resistance of tin-nickel electrodeposit impaired by pseudomorphic porosity originating on cold-rolled steel surface (left). Panel on right has had the shattered grain surface removed by chemical polishing (0-125 iim removed). Coating thickness 15 iim-, panels exposed 6 months to marine atmospheric corrosion (Hayling Island)...

The unfortunate action of the compound layer is observed only rarely, usually in hot water. In cooking vessels (domestic or industrial) the copper is protected satisfactorily at some sacrifice of tin, and occasional re-tinning ensures long service. In atmospheric corrosion the arrival of compounds at the surface of the coating results in some darkening and in loss of solderability. 

Atmospheric corrosion can be prevented by using volatile inhibitors which need not be applied directly to the surfaces to be protected. Most such inhibitors are amine nitrites, benzoates, chromates, etc. They are mainly used with ferrous metals. There is still some disagreement as to the mechanism of action. Clearly, any moisture that condenses must be converted to an inhibitive solution. There is no doubt that the widely used volatile inhibitors are effective in aqueous solutions containing moderate... 

A wide range of paints and other organic coatings is used for the protection of mild steel structures. Paints are used mainly for protection from atmospheric corrosion. Special chemically resistant paints have been developed for use on chemical process equipment. Chlorinated rubber paints and epoxy-based paints are used. In the application of paints and other coatings, good surface preparation is essential to ensure good adhesion of the paint film or coating. 

Time of wetness (TOW), considered as the time during which the corrosion process occurs, is an important parameter to study the atmospheric corrosion of metals. According to ISO-9223 standard, TOW is approximately the time when relative humidity exceeds 80% and temperature is higher than 0°C. No upper limit for temperature is established. In tropical climates, when temperature reaches values over 25°C, evaporation of water plays an important role and the possibility to establish an upper limit respecting temperature should be analyzed. The concept of TOW assumes the presence on the metallic surface of a water layer however, there are recent reports about the formation of water microdrops during the initial periods of atmospheric corrosion, showing that the idea of the presence of thin uniform water layers is not completely in agreement with the real situation in some cases (particularly indoor exposures). 

Most of the research carried out to study the initial stages of atmospheric corrosion have been made on a clean surface without corrosion products however, the metal is very often covered by thin or thick corrosion products after a given exposure time and these products usually act as retarders of the corrosion process. 

Taking into account the electrochemical nature of the atmospheric corrosion process it is absolutely necessary to use the concept of Time of Wetness (TOW). It is a concept commonly used in atmospheric corrosion of metallic materials and refers to the time when the metal is sufficiently wet for corrosion reaction to occur, that is, when an electrolyte is present in the metallic surface. Under the particular characteristics of atmospheric corrosion there are time periods where corrosion could not occur due to the absence of an electrolyte in the metallic surface. The lowest outdoor TOW values are observed in the desert regions, as also in the Antarctic and Arctic regions. Atmospheric corrosion rates of metals at these climatic conditions are also very low and in the case of cold regions, the increase of temperature leads to the increase of TOW and corrosion rate [11], In principle, TOW is a parameter that depends upon both the climatic conditions and in the characteristics of the metallic surface. 

The definition of TOW presented on ISO standard 9223 is the following The period during which a metallic surface is covered by adsorptive and/or liquid films of electrolyte that are capable of causing atmospheric corrosion .. In addition, the new document ISO WD/9223... 

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],... 

Almost all tests carried out to study the starting process of atmospheric corrosion have been performed in a surface without corrosion products however, in real conditions, the metal is covered with corrosion products after a given time and these products begin to play its role as retarders of the corrosion process in almost all cases. Corrosion products acts as a barrier for oxygen and contaminants diffusion, the free area for the occurrence of the corrosion is lower however, the formation of the surface electrolyte is enhanced. Only in very polluted areas the corrosion products accelerate the corrosion process. Water adsorption isoterms were determined to corrosion products formed in Cuban natural atmospheres[21]. Sorption properties of corrosion products (taking into account their salt content-usually hygroscopics) determine the possibilities of surface adsorption and the possibility of development of corrosion process... 

Under indoor conditions, in the same way than outdoors, it is necessary the presence of surface humidity for corrosion to occur due to the electrochemical nature of the atmospheric corrosion process however, in indoor conditions there are no precipitations and the presence of surface water depends mainly on water content in the air and changes in temperature on the surface, as well as the presence of hygroscopic substances on the metallic surface. 

Recent reports about the microdroplets formation in the starting periods of atmospheric corrosion [15-18] show that the idea of a thin uniform water layers is not completely in accordance with the reality. It has been observed that when a water drop is on the metallic surface, formed in the place where a salt deposit existed before, microdroplets are formed around this central drop. The cathodic process takes place in these surrounding microdroplets, meanwhile the anodic process takes place in the central drop. This idea is not consistent with the proposal of an uniform water layer on the surface and it is very probable that this situation could be obtained under indoor conditions. It has been determined that microdrops (about 1 micron diameter) clusters are formed around a central drop. An important influence of air relative humidity is reported on microdrops formation. There is a critical value of relative humidity for the formation of microdroplets. Under this value no microdroplets are formed. This value could be considered as the critical relative humidity. This situation is very similar to the process of indoor atmospheric corrosion presence of humid air, deposition of hygroscopic contaminants in the surface, formation of microdrops. Water is necessary for corrosion reaction to occur, but the reaction rate depends on the deposition rate and nature of contaminants. 

The atmospheric corrosion rate of metals depends mainly on TOW and pollutants however, if the differences in the corrosion process between outdoor and indoor conditions are taken into account, the influence of direct precipitation such as rain is very important for outdoor and negligible for indoor conditions. The acceleration effect of pollutants could change depending on wetness conditions of the surface, so the influence of the rain time and quantity should be very important in determining changes in corrosion rate. 

The adsorption isotherms for metallic surfaces are reported in the literature however, an important part of the atmospheric corrosion process takes place under rust layers, which play a decisive role in the long-term course of corrosion because of its sorption capacity for water. The influence of the chloride and sulfate anions has a real effect only when the corrosion products layer is already formed. Thus, the adsorption isotherms of the steel corrosion products formed in different atmospheres were determined. 

The concept of TOW assumes the presence on the metallic surface of a water layer however, there are recent reports about the formation of water microdrops during the initial periods of atmospheric corrosion, showing that the idea of the presence of thin uniform water layers is not completely in agreement with the real situation in some cases (particularly indoor exposures). 

The few reported cases concerning other metals, like zinc, aluminum, and magnesium, attest their susceptibility to corrosion due to volatile compounds in the museum environment [271]. Iron is naturally vulnerable to atmospheric corrosion whatever the pollutants, and the conservation of ferrous artifacts implicates a precise control of relative humidity, often requiring a surface protection like varnish, wax, or oil [272]. 

Heterogeneous reaction at the interface between a solid surface and the adjacent gas is central to many chemical processes. Examples include deposition or etching of materials, atmospheric corrosion, combustion of solids, and heterogeneous catalysis. 

Corrosion attributable to oxygen is deemed to result from the solution or oxygen by a thin film of liquid adjacent to the metallic surface, the transportation of the oxygen through the film, and the subsequent reaction at the surface of the metal. This explains why there is corrosive action even in relatively arid land. In a very dry atmosphere corrosion Is. however, markedly reduced. 

Copper. This element is beneficial to atmospheric corrosion resistance if preseni in amounts in excess of 0.2057. Appreciable amounts of copper are detrimental to hot-working operations. Copper also adversely affects forge welding and is detrimental to surface quality. However, copper does... 

While the chemical resistance varies somewhat, stainless steel is fairly resistant to most acids and bases, is not amalgamated by mercury, and is generally resistant to oxidizing agents. While it can be used in fluorine handling, Monel and nickel are much better for this purpose. The resistance of stainless steel to atmospheric corrosion is an advantage in vacuum work because a corroded surface tends to outgas. 

ASTM G84, Standard Practice for Measurement of Time-of-Wetness on Surfaces Exposed to Wetting Conditions as in Atmospheric Corrosion Testing, West Conshohoken, PA, 1993. 

Uses.—Palladium is seldom used in the pure state, and its alloys have hitherto received but little application even in scientific work, although recently a useful field has been discovered for utilising certain alloys, such as those of palladium and gold, as substitutes for platinum. They have been used, on account of their excellent resistance to atmospheric corrosion, for certain astronomical and dental purposes, and for coating the surfaces of reflectors used for searchlights, etc. Palladium salts are used in photography. 

Copper is commonly used in sheets as a roofing material when, upon exposure to the atmosphere, the surface becomes covered with a basic film of copper carbonate and/or sulphate. This gives rise to the familiar green patina of such roofs. Heavily polluted atmospheres, however, cause the film to be thicker and less adherent, in which case corrosion rates are high and film spalling will occur, exposing fresh metal surface to the corrosive atmosphere. 

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