The corrosion process

Once the passive layer breaks down then areas of rust will start appearing on the steel snrface. The chemical reactions are the same whether corrosion occnrs by chloride attack or carbonation. When steel in concrete corrodes it dissolves in the pore water and gives up electrons  

The two electrons (2e ) created in the anodic reaction must be consumed elsewhere on the steel surface to preserve electrical neutrality. In other words we cannot have large amounts of electrical charge building up at one place on the steel. There must be another chemical reaction to consume the electrons. This is a reaction that consumes water and oxygen  

The anodic and cathodic reactions ((2.1) and (2.2)) are only the first steps in the process of creating rust. However, this pair of reactions is critical to the understanding of corrosion and is widely quoted in any discussion on corrosion and corrosion prevention for steel in concrete. The reactions will be referred to often in this book. 

If the iron were just to dissolve in the pore water (the ferrous ion Fe in equation (2.1) is soluble) we would not see cracking and spalling of the concrete. Several more stages must occur for rust to form. This can be expressed in several ways and one is shown here where ferrons 

Fe + 20H - Fe(OH)2 Ferrous hydroxide 4Fe(OH)2 + O2 + 2H2O - 4Fe(OH)2 Ferric hydroxide 2Fe(OH)2 F6203 H2O + 2H2O Hydrated ferric oxide (rust) 

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Figure A3.10.1 (a) A schematic illustration of the corrosion process for an oxygen-rich water droplet on an iron surface, (b) The process can be viewed as a short-circuited electrochemical cell [4],...

Conserva.tlon, Because the most common conservation problem with metal objects occurs when corrosion processes form a threat to the safety of the object or disfigure its appearance to an unacceptable degree (130,131), many conservation treatments are intended to stabilize the corrosion processes and to remove aesthetically displeasing corrosion cmsts. The latter requkes a great deal of thought and discussion as to when a corrosion layer ceases to be a deskable patina and becomes unacceptable. 

Tantalum is not resistant to substances that can react with the protective oxide layer. The most aggressive chemicals are hydrofluoric acid and acidic solutions containing fluoride. Fuming sulfuric acid, concentrated sulfuric acid above 175°C, and hot concentrated aLkaU solutions destroy the oxide layer and, therefore, cause the metal to corrode. In these cases, the corrosion process occurs because the passivating oxide layer is destroyed and the underlying tantalum reacts with even mild oxidising agents present in the system. 

The mechanisms of lead corrosion in sulfuric acid have been studied and good reviews of the Hterature are available (27—30). The main techniques used in lead corrosion studies have been electrochemical measurements, x-ray diffraction, and electron microscopy. More recendy, laser Raman spectroscopy and photoelectrochemistry have been used to gain new insight into the corrosion process (30,31). 

In maldug electrochemical impedance measurements, one vec tor is examined, using the others as the frame of reference. The voltage vector is divided by the current vec tor, as in Ohm s law. Electrochemical impedance measures the impedance of an electrochemical system and then mathematically models the response using simple circuit elements such as resistors, capacitors, and inductors. In some cases, the circuit elements are used to yield information about the kinetics of the corrosion process. 

Sulfides are intermixed with iron oxides and hydroxides on carbon steels and cast irons. The oxides are also produced in the corrosion process (Reaction 6.6). Although theoretical stoichiometry of 1 to 3 is often suggested between sulfide and ferrous hydroxide, empirically the ratio of iron sulfide to ferrous hydroxide is highly variable. Sulfide decomposes spontaneously upon exposure to moist air. Additionally, corrosion-product stratification is marked, with sulfide concentration being highest near metal surfaces. 

Perhaps the most important stress factor affecting corrosion fatigue is the frequency of the cyclic stress. Since corrosion is an essential component of the failure mechanism and since corrosion processes typically require time for the interaction between the metal and its environment, the corrosion-fatigue life of a metal depends on the frequency of the cyclic stress. Relatively low-stress frequencies permit adequate time for corrosion to occur high-stress frequencies may not allow sufficient time for the corrosion processes necessary for corrosion... 

Chemical removal of deposits and corrosion products revealed the appearance of the groove (Fig. 14.5). The crevice formed by the incompletely fused weld seam fostered the establishment of differential concentration cells (see Chap. 2). This resulted in localized corrosion and eventual perforation through the greatly thinned tube wall at the bottom of the crevice. The tubercle, which is composed of corrosion products, is a simple result of the corrosion process occurring locally within the crevice. 

The triggering mechanism for the corrosion process was localized depassivation of the weld-metal surface. Depassivation (loss of the thin film of chromium oxides that protect stainless steels) can be caused by deposits or by microbial masses that cover the surface (see Chap. 4, Underdeposit Corrosion and Chap. 6, Biologically Influenced Corrosion ). Once depassivation occurred, the critical features in this case were the continuity, size, and orientation of the noble phase. The massive, uninterrupted network of the second phase (Figs. 15.2 and 15.21), coupled... 

Galvanic corrosion in typical industrial cooling water systems is the net result of the interplay of these factors. Some factors may accelerate the corrosion process others may retard it. In their approximate order of importance, the more influential factors are discussed below. 

All areas of the cooling water system where a specific form of damage is likely to be found are described. The corrosion or failure causes and mechanisms are also described. Especially important factors influencing the corrosion process are listed. Detailed descriptions of each failure mode are given, along with many common, and some not-so-common, case histories. Descriptions of closely related and similarly appearing damage mechanisms allow discrimination between failure modes and avoidance of common mistakes and misconceptions. 

We can aggravate the corrosion effect if misiiligned parts have relative movement, sueh as loose fit bearings or rapid changes in the system. Cavitation, erosion and high fluid velocity advance the corrosion process. 

The concept of the corrosion process, derived from the Latin corrodere (to eat away, to destroy), first appeared in the Philosophical Transactions in 1667 [2]. It was discussed in a German translation from the French on the manufacture of white lead in 1785 and was mentioned in 1836 in the translation of an English paper by Davy on the cathodic protection of iron in seawater [3]. However, almost until the present day, the term was used indiscriminately for corrosion reaction, corrosion effects, and corrosion damage. Only in DIN 50900, Part I, were these terms distinguished and defined [4] (see Section 2.1). 

Electrical conductivity is of interest in corrosion processes in cell formation (see Section 2.2.4.2), in stray currents, and in electrochemical protection methods. Conductivity is increased by dissolved salts even though they do not take part in the corrosion process. Similarly, the corrosion rate of carbon steels in brine, which is influenced by oxygen content according to Eq. (2-9), is not affected by the salt concentration [4]. Nevertheless, dissolved salts have a strong indirect influence on many local corrosion processes. For instance, chloride ions that accumulate at local anodes can stimulate dissolution of iron and prevent the formation of a film. Alkali ions are usually regarded as completely harmless, but as counterions to OH ions in cathodic regions, they result in very high pH values and aid formation of films (see Section 2.2.4.2 and Chapter 4). 

Corrosion protection measures are divided into active and passive processes. Electrochemical corrosion protection plays an active part in the corrosion process by changing the potential. Coatings on the object to be protected keep the aggressive medium at a distance. Both protection measures are theoretically applicable on their own. However, a combination of both is requisite and beneficial for the following reasons ... 

Coatings of less noble metals than the substrate metal (e.g., Zn on Fe) are only protective if the corrosion product of the metal coating restricts the corrosion process. At the same time, the formation of aeration cells is hindered by the metal coating. No corrosion occurs at defects. Additional cathodic protection to reduce the corrosion of the metal coating can be advantageous. Favorable polarization properties and low protection current requirements are possible but need to be tested in individual cases. The possibility of damage due to blistering and cathodic corrosion must be heeded. 

A higher content of AI2O3 and SiOj is critical for the composition of the protective films in the tubing, assuming the water contains silicates or silicic acid. The protective films have a maximum thickness of 1.5 mm and cannot grow further. The corrosion process can be stopped even in copper pipe networks with type I pitting [21] by providing a reaction tank with impressed current aluminum anodes. 

Change in viscosity may affect the circulation, diffusion and other properties pertinent to the corrosion process. 

For the corrosion process to proceed, the corrosion cell must contain an anode, a cathode, an electrolyte and an electronic conductor. When a properly prepared and conditioned mud is used, it causes preferential oil wetting on the metal. As the metal is completely enveloped and wet by an oil environment that is electrically nonconductive, corrosion does not occur. This is because the electric circuit of the corrosion cell is interrupted by the absence of an electrolyte. Excess calcium hydroxide [Ca(OH)j] is added as it reacts with hydrogen sulfide and carbon dioxide if they are present. The protective layer of oil film on the metal is not readily removed by the oil-wet solids as the fluid circulates through the hole. 

Arctic Drilling. Corrosion problems encountered in arctic area drilling are no different from problems faced in other areas of the world. It is a general misconception that during arctic drilling corrosion-related problems are either not very severe or totally absent due to low temperatures. Cool temperatures may slow down the corrosion process. However, they also increase the solubility of oxygen, carbon dioxide and hydrogen sulfide. Therefore, the net result can be an increase in the rate of corrosion. While cold temperatures may cause problems, the temperature fluctuation common in arctic environments can be a more severe source of corrosion-related problems [215]. 

The thermodynamic driving force behind the corrosion process can be related to the corrosion potential adopted by the metal while it is corroding. The corrosion potential is measured against a standard reference electrode. For seawater, the corrosion potentials of a number of constructional materials are shown in Table 53.1. The listing ranks metals in their thermodynamic ability to corrode. Corrosion rates are governed by additional factors as described above. 

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. 

Oxygen from the atmosphere, dissolved in the electrolyte solution provides the cathode reactant in the corrosion process. Since the electrolyte solution is in the form of thin films or droplets, diffusion of oxygen from the atmosphere/electrolyte solution interface to the solution/metal interface is rapid. Moreover, convection currents within these thin films of solution may play a part in further decreasing concentration polarisation of this cathodic process . Oxygen may also oxidise soluble corrosion products to less soluble ones which form more or less protective barriers to further corrosion, e.g. the oxidation of ferrous species to the less soluble ferric forms in the rusting of iron and steel. 

In recent years the mechanism of crevice has been mathematically modelled and a more thorough understanding of the corrosion processes has been evolved . From such mathematical modelling it is feasible to predict critical crevice dimensions to avoid crevice corrosion determined with relatively simple electrochemical measurements on any particular stainless steel. 

Hardly any quantitative results on the effect of movement on corrosion of steel are available. Water movement can markedly affect the corrosion process in controlling the rate of transport of reactants to the corrosion site, and the removal of the corrosion reaction products. 

SOIL IN THE CORROSION PROCESS Aeration and Oxygen Diffusion... 

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