Corrosion Fundamentals

1. Corrosion Fundamentals One of the key factors in any corrosion situation is the environment. The definition and characteristics of this variable can be quite complex. For practical, it is important to realize that the environment is a variable that can change with time and conditions. Environment that actually affects a metal corresponds to the microenvironmental conditions that this metal really “sees,” i.e., the local environment at the surface of the metal. It is indeed the reactivity of this local environment that will determine the real corrosion damage. Thus, an experiment that investigates only the nominal environmental condition without consideration of local effects is useless for lifetime prediction.

2. water • In our societies, water is used for a wide variety of purposes, from supporting life as potable water to performing a multitude of industrial tasks such as heat exchange and waste transport. • The impact of water on the integrity of materials is thus an important aspect of system management. Since steels and other iron-based alloys are the metallic materials most commonly exposed to water, aqueous corrosion will be discussed with a special focus on the reactions of iron (Fe) with water (H2O). • Metal ions go into solution at anodic areas in an amount chemically equivalent to the reaction at cathodic areas (Fig. 1.1).

3. Reaction

4. Anodic Reaction • In the cases of iron-based alloys, the following reaction usually takes place at anodic areas:

5. Cathodic Reaction • When iron corrodes, the rate is usually controlled by the cathodic reaction, which in general is much slower (cathodic control). • In de-aerated solutions, the cathodic reaction is

6. The cathodic reaction proceeds rapidly in acids, but only slowly in alkaline or neutral aqueous media. The corrosion rate of iron in deaerated neutral water at room temperature, for example, is less than 5 μm/year. The rate of hydrogen evolution at a specific pH depends on the presence or absence of low-hydrogen overvoltage impurities in the metal.

7. The cathodic reaction can be accelerated by the reduction of dissolved oxygen in accordance with the following reaction, a process called depolarization:

8. Dissolved oxygen reacts with hydrogen atoms adsorbed at random on the iron surface, independent of the presence or absence of impurities in the metal. The oxidation reaction proceeds as rapidly as oxygen reaches the metal surface. Adding (1.1) and (1.3), making use of the reaction H2O H+ + OH-, leads to reaction (1.4),

9. Diffusion-barrier Layer Hydrous ferrous oxide (FeO . nH2O) or ferrous hydroxide [Fe(OH)2] composes the diffusion-barrier layer next to the iron surface through which O2 must diffuse. The pH of a saturated Fe(OH)2 solution is about 9.5, so that the surface of iron corroding in aerated pure water is always alkaline. The color of Fe(OH)2, although white when the substance is pure, is normally green to greenish black because of incipient oxidation by air.

10. At the outer surface of the oxide film, access to dissolved oxygen converts ferrous oxide to hydrous ferric oxide or ferric hydroxide, in accordance with Hydrous ferric oxide is orange to red-brown in color and makes up most of ordinary rust. It exists as nonmagnetic Fe2O3 (hematite) or as magnetic Fe2O3, the  form having the greater negative free energy of formation (greater thermodynamic stability). Saturated Fe(OH)3 is nearly neutral in pH. A magnetic hydrous ferrous ferrite, Fe3O4 . nH2O, often forms a black intermediate layer between hydrous Fe2O3 and FeO. Hence rust films normally consist of three layers of iron oxides in different states of oxidation.

11. Applications of Potential-pH Diagrams E-pH or Pourbaix diagrams are a convenient way of summarizing much thermodynamic data and provide a useful means of summarizing the thermodynamic behavior of a metal and associated species in given environmental conditions. E-pH diagrams are typically plotted for various equilibria on normal cartesian coordinates with potential (E) as the ordinate (y axis) and pH as the abscissa (x axis).

12. Applications of Potential-pH Diagrams • For corrosion in aqueous media, two fundamental variables, namely corrosion potential and pH, are deemed to be particularly important. • Changes in other variables, such as the oxygen concentration, tend to be reflected by changes in the corrosion potential. • Considering these two fundamental parameters, Staehle introduced the concept of overlapping mode definition and environmental definition diagrams, to determine under what environmental circumstances a given mode/submode of corrosion damage could occur (Fig. 1.2).

13. Overlapping Modes

14. Applications of Potential-pH Diagrams • In the application of E-pH diagrams to corrosion, thermodynamic data can be used to map out the occurrence of corrosion, passivity, and nobility of a metal as a function of pH and potential. The operating environment can also be specified with the same coordinates, facilitating a thermodynamic prediction of the nature of corrosion damage. • A particular environmental diagram showing the thermodynamic stability of different chemical species associated with water can also be derived thermodynamically. This diagram, which can be conveniently superimposed on E-pH diagrams, is shown in Fig. 1.3. While the E-pH diagram provides no kinetic information whatsoever, it defines the thermodynamic boundaries for important corrosion species and reaction

15. Figure 1.3 Thermodynamic stability of water, oxygen, and hydrogen. (A is the Equilibrium line for the reaction: H2 = 2H+ + 2e-. B is the equilibrium line for the reaction: 2H2O = O2 + 4H+ + 4e-. * indicates increasing thermodynamic driving force for cathodic oxygen reduction, as the potential falls below line B. ** indicates increasing thermodynamic driving force for cathodic hydrogen evolution, as the potential falls below line A.)

16. Observed Corrosion The observed corrosion behavior of a particular metal or alloy can also be superimposed on E-pH diagrams. Such a superposition is presented in Fig. 1.4. The corrosion behavior of steel presented in this figure was characterized at different potentials in solutions with varying pH levels.

17. Thermodynamic boundaries of the types of corrosion observed on steel

18. Corrosion of steel in water at elevated temperatures Many phenomena associated with corrosion damage to iron-based alloys in water at elevated temperatures can be rationalized on the basis of iron-water E-pH diagrams. Marine boilers on ships and hot-water heating systems for buildings are relevant practical examples

19. Marine boilers • Two important variables affecting water-side corrosion of iron-based alloys in marine boilers are the pH and oxygen content of the water. • As the oxygen level has a strong influence on the corrosion potential, these two variables exert a direct influence in defining the position on the E pH diagram. A higher degree of aeration raises the corrosion potential of iron in water, while a lower oxygen content reduces it.

20. Elevated-temperature and Ambient-temperature • When considering the water-side corrosion of steel in marine boilers, both the elevated-temperature and ambient-temperature cases should be considered, since the latter is important during shutdown periods. Boiler feedwater treatment is an important element of minimizing corrosion damage

21. A fundamental treatment requirement is maintaining an alkaline pH value, ideally in the range of 10.5 to 11 at room temperature. This precaution takes the active corrosion field on the left-hand side of the E-pH diagrams out of play, as shown in the E-pH diagrams drawn for steel at two temperatures, 25°C (Fig. 1.5) and 210°C (Fig. 1.6).

22. E-pH diagram of iron in water at 25°C and its observed corrosion behavior

23. Corrosion forms of Steel in Water

24. E-pH diagram of iron in water at 210°C

25. Observations of Figure 1.5 • At the recommended pH levels, around 11, the E-pH diagram in Fig. 1.5 indicates the presence of thermodynamically stable oxides above the zone of immunity. • It is the presence of these oxides on the surface that protects steel from corrosion damage in boilers.

26. Practical Observations Practical Practical experience related to boiler corrosion kinetics at different feed water pH levels is included in Fig. 1.5. The kinetic information in Fig. 1.5 indicates that high oxygen contents are generally undesirable. It should also be noted from Figs. 1.5 and 1.6 that active corrosion is possible in acidified untreated boiler water, even in the absence of oxygen.

27. Localized Pitting Inspection of the kinetic data presented in Fig. 1.5 reveals a tendency for localized pitting corrosion at feed water pH levels between 6 and 10. This pH range represents a situation in between complete surface coverage by protective oxide films and the absence of protective films.

28. Localized anodic dissolution is to be expected on a steel surface covered by a discontinuous oxide film, with the oxide film acting as a cathode. • Another type of localized corrosion, caustic corrosion, can occur when the pH is raised excessively on a localized scale. The E-pH diagrams in Figs. 1.5 and 1.6 indicate the possibility of corrosion damage at the high end of the pH axis, where the protective oxides are no longer stable. • Such undesirable pH excursions tend to occur in high temperature zones, where boiling has led to a localized caustic concentration. • A further corrosion problem, which can arise in highly alkaline environments, is caustic cracking, a form of stress corrosion cracking. Examples in which such microenvironments have been proven include seams, rivets, and boiler tube-to-tube plate joints.

29. Another Example Hydronic Heating of Buildings

30. Figure 1.7 E-pH diagram of iron in water at 25°C, highlighting the corrosion processes in the hydronic pH range

31. Figure 1.8 E-pH diagram of iron in water at 85°C (hydronic system

32. Hydronic Heating of Buildings • Given a pH range for mains water of 6.5 to 8 and the E-pH diagrams in Figs. 1.7 (25°C) and 1.8 (85°C), it is apparent that minimal corrosion damage is to be expected if the corrosion potential remains below _0.65 V (SHE). • The position of the oxygen reduction line indicates that the cathodic oxygen reduction reaction is thermodynamically very favorable.

33. Role of Oxygen Content • From kinetic considerations, the oxygen content will be an important factor in determining corrosion rates. • The oxygen content of the water is usually minimal, since the solubility of oxygen in water decreases with increasing temperature (Fig. 1.9), and any oxygen remaining in the hot water is consumed over time by the cathodic corrosion reaction. • Typically, oxygen concentrations stabilize at very low levels (around 0.3 ppm), where the cathodic oxygen reduction reaction is stifled and further corrosion is negligible.

34. Figure 1.9 Solubility of oxygen in water in equilibrium with air at different temperatures.

35. Role of Oxygen Content • Higher oxygen levels in the system drastically change the situation, potentially reducing radiator lifetimes by a factor of 15. • The undesirable oxygen pickup is possible during repairs, from additions of fresh water to compensate for evaporation, or, importantly, through design faults that lead to continual oxygen pickup from the expansion tank. • The higher oxygen concentration shifts the corrosion potential to higher values, as shown in Fig. 1.7. Since the Fe(OH)3 field comes into play at these high potential values, the accumulation of a red-brown sludge in radiators is evidence of oxygen contamination.

36. Hydrogen Production • From the E-pH diagrams in Figs. 1.7 and 1.8, it is apparent that for a given corrosion potential, the hydrogen production is thermodynamically more favorable at low pH values. • The production of hydrogen is, in fact, quite common in microenvironments where the pH can be lowered to very low values, leading to severe corrosion damage even at very low oxygen levels. • The corrosive microenvironment prevailing under surface deposits is very different from the bulk solution. In particular, the pH of such microenvironments tends to be very acidic.