CHAPTER 8 CORROSION

8.1 8.2 ELECTROCHEMICAL REACTIONS FORMS OF CORROSION 8.2.1 8.2.2 8.2.3 8.3 Galvanic Corrosion Differential Aeration Corrosion Other Concentration Cells

The performance of a material must be evaluated in the context of its interaction with its service environment. Such interactions may be mechanical (friction and wear), or electrochemical (oxidation and corrosion). These interactions usually result in the degradation of the material (i.e. deterioration in mechanical and/or physical properties, or appearance), leading to huge economic losses (5% or more of the GDP of industrialized countries), as well as posing threats to human safety.

PROTECTION AGAINST CORROSION

(a) Fresh water

(b) Salt water

NITRIC ACID

PETROL

(c) Acids and alkalis

(d) Organic solvents

(e) Oxidation

(f) UV radiation

Fig. 8.1-1 Materials undergo electrochemical interactions with water, acids and alkalis, organic solvents, oxygen and radiation. 8-1 8-2

Corrosion occurs in an aqueous environment, and together with wear, are the main causes of metal degradation at ambient temperatures. Generally, corrosion will occur in air with relative humidity (RH) greater than 60-70%, which forms an invisible thin film of moisture on the surface of metal.

The magnitude of this potential depends on the tendency of the metal to dissolve into the electrolyte. The stronger the tendency, the more negative the potential. When a different metal, C, is added to the same electrolyte
(Fig. 8.1-2b),

it also develops its own potential, depending on

its tendency for metal dissolution.

8.1

ELECTROCHEMICAL REACTIONS

If the two metals were connected by a wire

(Fig. 8.1-2c),

the

excess electrons would try to minimize the potential When immersed in an electrolyte, most metals have varying degrees of tendency to dissolve into the electrolyte as positively-charged metal ions, leaving behind the negatively-charged electrons in the metal (Fig. 8.1-2a). The metal, A, now negatively-charged, will attract positive ions in the electrolyte in its vicinity, such that the metal ions that have just dissolved in the electrolyte tend to revert back to solid metal atoms again. In the absence of external influences, an equilibrium is reached in which metal atoms and ions are continually entering and leaving the electrolyte at the metal surface. Overall, there is no net change in the system, but the metal has developed an electrochemical potential.
8-3 Fig. 8.1-2 (a) Metal A at equilibrium with positive metal ions in solution, adjacent to the electrons left behind. (b) Metal C has less tendency to dissolve in the electrolyte, leaving less negative charge in the metal. (c) A wire conncection allows electrons to flow from the more negative to the less negative metal. As electrons flow, metal A becomes less negative and metal C becomes more negative. 8-4

difference by distributing themselves around the system. Electrons flow from the metal with more excess electrons (more negative potential), A, to the metal with fewer electrons (less negative potential), C.

 Since metal A now becomes less negatively-charged, there is less attraction between the metal and the positive ions in the electrolyte. Some of the metal ions drift away, upsetting the equilibrium around the metal surface and allowing further dissolution of metal A, i.e. A corrodes. Metal A is known as the anode, where electrons are produced through the following reaction: M ! M + ne
n+

In order for corrosion to occur in a system, a potential difference must exist between different regions, which must also be electrically connected, such that electrons produced at the anode can be consumed at the cathode. An electrolyte must also be present for the conduction of ions. If any of these elements were missing, the corrosion reaction would stop. The potentials of various metals under standard conditions have been measured relative to a hydrogen electrode and are listed in the electrochemical series
(Table 8.1-2).

(anodic/oxidation reaction)

On the other hand, metal C has gained electrons to become more negatively-charged and its positive ions in the electrolyte are thus more strongly attracted to the metal and may even convert back into solid metal atoms. The electrons from A are consumed through various reactions at C, called the cathode, depending on the electrolyte. Some cathodic/reduction reactions are:
Table 8.1-1 Some common cathode reactions for aqueous galvanic cells.

A metal

that is lower on the electrochemical series has a greater tendency to lose electrons and become metal ions in solution (i.e. corrode).
Table 8.1-2 Standard electrochemical potentials.

8-5

8-6

 The potential of a metal depends on many factors, such as temperature, type of electrolyte, concentration of metal ions and other species (e.g. oxygen) in the electrolyte, etc. The electrochemical series was generated under highly idealized conditions; in most practical situations, the potential of a metal differs from its value in this series. It is thus more useful to refer to the experimental galvanic series, which is a simple, qualitative ranking of the relative reactivities of a number of metals and commercial alloys in a particular environment, e.g. seawater (Table 8.1-3).
Table 8.1-3 The galvanic series in aerated seawater at 25C.

8.2
8.2.1

FORMS

OF

CORROSION

Galvanic Corrosion

Galvanic corrosion occurs when two metals of different compositions are electrically connected in an electrolyte. The alloy with the more negative potential becomes the anode and corrodes, while the less negative metal acts as the cathode. Generally, the greater the potential difference, the more severe corrosion would be. Since the same total number of electrons must flow through the anodic and cathodic regions during corrosion, the ratio of anodic to cathodic surface area will affect the rate of corrosion. Small anodes in contact with large cathodes will corrode more severely than large anodes in contact with small cathodes (Fig. 8.2-1).

Fig. 8.2-1 Effects of anode-to-cathode area: (a) A large cathode (Cu) area consumes a large number of electrons during the cathodic reaction, which would have to be provided by the severe corrosion of the small anode (Fe). (b) Corrosion is less severe when the ratio of the anode to cathode surface area is large (i.e. large anodesmall cathode is favourable). 8-7 8-8

 Uniform corrosion is a special case of galvanic corrosion occurring at the microscopic level within the same metal. Even a nominally homogeneous metal surface contains tiny variations in composition and structure, giving rise to microscopic local anodes and cathodes. With time, the locations of the anodic and cathodic regions change randomly so that the result is a uniform loss of metal over the entire exposed surface. Alloys containing more than one phase
(Sec. 9.1)

Intergranular corrosion could also arise from precipitates forming at grain boundaries. In alloys containing elements that offer corrosion protection (e.g. stainless steel), such precipitation reactions at the grain boundaries deplete adjacent areas of solute, resulting in these areas being less corrosion resistant than (i.e. anodic to) the surrounding grain material (Fig. 8.2-3).

would

similarly undergo microscopic galvanic corrosion

(Fig 8.2-2),

since each phase has a different composition. Single-phase alloys are generally more resistant to corrosion than multiphase ones.
(a) (b) Fig. 8.2-3 (a) Intergranular corrosion due to carbide precipitation at the grain boundary. (b) Variation of Cr content in the vicinity of grain boundaries precipitates in stainless steel. Fig. 8.2-2 Microscopic galvanic corrosion in steel (a two-phase alloy).

In some cases of intergranular corrosion, individual grains are loosened and

(Fig. 8.2-4).

lost loss

from of

the grain

Galvanic couples may develop at grain boundaries, leading to intergranular corrosion. The segregation of impurities at grain boundaries could make these regions anodic to the bulk of the grains.
8-9

material the

In other cases,

localized

boundary material can lead to an appearance similar to cracking.

Fig. 8.2-4 Intergranular corrosion in stainless steel. 8-10

8.2.2

Differential Aeration Corrosion

In many instances, oxygen is required at the cathode in order for corrosion to occur [See Table 8.1-1, cathode reactions 3 and 4]. If there is a difference in oxygen concentration between two regions, the area of low oxygen concentration will become the anode, while the region of high oxygen concentration will act as the cathode. Differential aeration is responsible for crevice corrosion and pitting corrosion corrosion
(Fig. 8.2-5). (a) (b)

In these forms of localized

Fig. 8.2-5 (a) Crevice corrosion, and (b) pitting corrosion, due to differential aeration.

(localized as opposed to general or uniform corrosion, which

occurs everywhere on the metal surface),

the oxygen in small crevices

and pits are consumed during uniform corrosion. Since there is restricted exchange of electrolyte from within the confined spaces of these locations, these regions become lower in oxygen concentration than the rest of the material that is exposed to a large volume of electrolyte. As a result, corrosion occurs preferentially in the crevices and pits. Differential aeration is also the mechanism behind waterline corrosion. Oxygen is able to reach metal near the waterline than regions further away; thus, the metal just inside the waterline will become cathodic while the remaining immersed metal will become anodic (Fig. 8.2-6).
8-11 Fig. 8.2-6 Waterline corrosion beneath a drop of water. Fig. 8.2-7 Corrosion is more severe in (a) sandy soil than in (b) clay, due to the permeability of sand to oxygen.

An environment in which oxygen is severely limited will reduce corrosion significantly (Fig. 8.2-7).
8-12

8.2.3

Other Concentration Cells

8.3

PROTECTION AGAINST CORROSION

A metal that has been cold worked contains a high density of dislocations. Since dislocations are associated with higher energy, these highly-stressed, cold-worked regions in a metal will act as anodes to less-stressed cathodic areas
(Fig. 8.2-8).

Corrosion can be retarded or prevented if either the anodic or cathodic reaction can be stifled. Many corrosion problems can be eliminated through proper design
(Fig. 8.3-1)

and material selection to minimize

concentration or galvanic differences. Materials that produce protective oxide layers, e.g. aluminium alloys (Al2O3) or stainless steels (Cr2O3), may be used instead.

Fig. 8.2-8 The regions of a nail that were stressed during fabrication or use are anodic and will corrode locally.

Fig. 8.2-9 The higher energy of grain boundaries makes them anodic and more susceptible to corrosion.

Similarly, grain boundaries, with their higher energy, are anodic to the bulk of the grains and tend to corrode more severely
(Fig. 8.2-9; see also Sec. 4.7 on Metallography). (Sec. 8.2-1),

However, unlike

intergranular corrosion

the rate of corrosion at

grain boundaries that do not contain segregated impurities or precipitates is not significantly higher than the grain interior, since the potential difference between the boundaries and interior is only minimal.
8-13 Fig. 8.3-1 Reducing crevice corrosion through improved design. 8-14

 Protective coatings prevent contact between the metal and electrolyte (e.g. paints, chrome-plating). Furthermore, if the coating is anodic to the underlying metal (e.g. Zn on steel or galvanized steel), should the coating become scratched, the metal will continue to be protected since the coating will corrode instead (Fig. 8.3-2).

Fig. 8.3-3 Cathodic protection through sacrificial zinc anodes on the steel hulls of ships.

Fig. 8.3-2 Zinc is anodic to steel, such that should the Zn coating become disrupted, the large anode (Zn) to small cathode (steel) area would ensure continued protection. However, steel is anodic to tin, which would result in a small anode-to-cathode area ratio if the coating is scratched; this is undesirable since it would cause severe corrosion of the steel.

Inhibitors may be used in closed systems. These are chemicals added to the electrolyte that usually form protective layers either on the surfaces of the anode or cathode. Other inhibitors may retard the cathodic reaction, thereby reducing rate of corrosion at the anode. Cathodic protection works by forcing the corroding metal to become the cathode instead. One way is to use a sacrificial anode by electrically connecting a more anodic metal to the metal to be protected. The more anodic metal corrodes in preference to the original metal The sacrificial anode would need to periodically.
8-15 (Fig. 8.3-3 & 4a). Fig. 8.3-4 Cathodic protection of underground pipelines using (a) sacrificial zinc anode, and (b) impressed current.

Another cathodic protection method similar to the sacrificial anode method is the use of an impressed current. Since an anode corrodes when electrons flow away, the anode can be made cathodic by supplying a larger counter-current to neutralize the corrosion current
(Fig 8.3-4b).

The major advantage of this method is that it is to use non-consumable anodes. Another

possible

be

replaced

advantage is that the supply may be controlled to regulate the current provided.
8-16