CHAPTER 8

The performance of a material must be evaluated in the

context of its interaction with its service environment. Such

CORROSION

interactions may be mechanical (friction and wear), or

electrochemical (oxidation and corrosion).
These interactions usually result in the degradation of the

8.1

ELECTROCHEMICAL REACTIONS

8.2

FORMS OF CORROSION

properties, or appearance), leading to huge economic

8.2.1

Galvanic Corrosion

losses (5% or more of the GDP of industrialized countries),

8.2.2

Differential Aeration Corrosion

as well as posing threats to human safety.

8.2.3

Other Concentration Cells

8.3

material (i.e. deterioration in mechanical and/or physical

PROTECTION AGAINST CORROSION

(a) Fresh water

NITRIC
ACID

(c) Acids and alkalis

(e) Oxidation

(b) Salt water

PETROL

(d) Organic solvents

(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

The magnitude of this potential depends on the tendency

together with wear, are the main causes of metal

of the metal to dissolve into the electrolyte. The stronger

degradation at ambient temperatures. Generally, corrosion

the tendency, the more negative the potential.

will occur in air with relative humidity (RH) greater than

60-70%, which forms an invisible thin film of moisture on

When a different metal, C, is added to the same electrolyte

(Fig. 8.1-2b),

the surface of metal.

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

difference by distributing themselves around the system.

varying degrees of tendency to dissolve into the electrolyte

Electrons flow from the metal with more excess electrons

as positively-charged metal ions, leaving behind the

(more negative potential), A, to the metal with fewer

negatively-charged electrons in the metal (Fig. 8.1-2a).

electrons (less negative potential), C.

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

 Since metal A now becomes less negatively-charged, there

In order for corrosion to occur in a system, a potential

is less attraction between the metal and the positive ions in

difference must exist between different regions, which

the electrolyte. Some of the metal ions drift away,

must also be electrically connected, such that electrons

upsetting the equilibrium around the metal surface and

produced at the anode can be consumed at the cathode.

allowing further dissolution of metal A, i.e. A corrodes.

An electrolyte must also be present for the conduction of

Metal A is known as the anode, where electrons are

produced through the following reaction:
n+

M ! M + ne

(anodic/oxidation reaction)

ions. If any of these elements were missing, the corrosion

reaction would stop.
The potentials of various metals under standard conditions

On the other hand, metal C has gained electrons to

have been measured relative to a hydrogen electrode and

become more negatively-charged and its positive ions in

are listed in the electrochemical series

the electrolyte are thus more strongly attracted to the

that is lower on the electrochemical series has a greater

metal and may even convert back into solid metal atoms.

tendency to lose electrons and become metal ions in

The electrons from A are consumed through various

reactions at C, called the cathode, depending on the

(Table 8.1-2).

A metal

solution (i.e. corrode).

Table 8.1-2 Standard electrochemical potentials.

electrolyte. Some cathodic/reduction reactions are:

Table 8.1-1 Some common cathode reactions for aqueous galvanic cells.

8-5

8-6

 The potential of a metal depends on many factors, such as

8.2

FORMS

OF

CORROSION

temperature, type of electrolyte, concentration of metal

ions and other species (e.g. oxygen) in the electrolyte, etc.

8.2.1

Galvanic Corrosion

The electrochemical series was generated under highly

idealized conditions; in most practical situations, the

Galvanic corrosion occurs when two metals of different

compositions are electrically connected in an electrolyte.

potential of a metal differs from its value in this series.

It is thus more useful to refer to the experimental galvanic

The alloy with the more negative potential becomes the

series, which is a simple, qualitative ranking of the relative

anode and corrodes, while the less negative metal acts as

reactivities of a number of metals and commercial alloys in

the

a particular environment, e.g. seawater (Table 8.1-3).

difference, the more severe corrosion would be.

cathode.

Generally,

the

greater

the

potential

Since the same total number of electrons must flow

Table 8.1-3 The galvanic series in aerated seawater at 25C.

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

Intergranular corrosion could also arise from precipitates

occurring at the microscopic level within the same metal.

forming at grain boundaries. In alloys containing elements

Even a nominally homogeneous metal surface contains tiny

that offer corrosion protection (e.g. stainless steel), such

variations in composition and structure, giving rise to

precipitation reactions at the grain boundaries deplete

microscopic local anodes and cathodes. With time, the

adjacent areas of solute, resulting in these areas being less

locations of the anodic and cathodic regions change

corrosion resistant than (i.e. anodic to) the surrounding

randomly so that the result is a uniform loss of metal over

grain material (Fig. 8.2-3).

the entire exposed surface.

Alloys containing more than one phase

(Sec. 9.1)

similarly undergo microscopic galvanic corrosion

would

(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

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.

loosened

and

material

(Fig. 8.2-4).

the

localized

lost

from

the

In other cases,
loss

of

grain

boundary material can lead to an

appearance similar to cracking.
Fig. 8.2-4 Intergranular corrosion in stainless steel.

8-9

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).

In these forms of localized

(a)

(b)

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).

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).

8-11

8-12

8.2.3

Other Concentration Cells

8.3

A metal that has been cold worked contains a high density

of dislocations. Since dislocations are associated with

PROTECTION AGAINST CORROSION

Corrosion can be retarded or prevented if either the anodic

or cathodic reaction can be stifled.

higher energy, these highly-stressed, cold-worked regions

in a metal will act as anodes to less-stressed cathodic areas

Many corrosion problems can be eliminated through

proper design

(Fig. 8.2-8).

(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).

intergranular corrosion

(Sec. 8.2-1),

However, unlike

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.

Fig. 8.3-1 Reducing crevice corrosion through improved design.

8-13

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

Fig. 8.3-4 Cathodic protection of underground pipelines using

(a) sacrificial zinc anode, and (b) impressed current.

protective layers either on the surfaces of the anode or

cathode. Other inhibitors may retard the cathodic reaction,

Another cathodic protection method similar to the

thereby reducing rate of corrosion at the anode.

sacrificial anode method is the use of an impressed

Cathodic protection works by forcing the corroding

current. Since an anode corrodes when electrons flow

metal to become the cathode instead. One way is to use a

away, the anode can be made cathodic by supplying a

sacrificial anode by electrically connecting a more anodic

larger counter-current to neutralize the corrosion current

metal to the metal to be protected. The more anodic metal

(Fig 8.3-4b).

corrodes in preference to the original metal

The

sacrificial

anode

would

need

to

(Fig. 8.3-3 & 4a).

be

replaced

periodically.

possible

The major advantage of this method is that it is

to

use

non-consumable

anodes.

Another

advantage is that the supply may be controlled to regulate

the current provided.

8-15

8-16