3.

Corrosion Mechanisms: Some Basic Understanding

1. General

Corrosion is the destructive attack upon a metal by its environment and it is probably the commonest
electrochemical phenomenon that is experienced in/day-to-day living.

For the practising engineer the most important aspect of corrosion science is probably corrosion-
prevention. However before appropriate protective or preventive measures can be outlined, it is
necessary to understand the basic principles ruling the corrosion phenomenon.

2. Basic Principles

2.1. Qualitative ideas

Metals occur in nature most commonly as oxide or sulphide ores in which they are in a higher
oxidation state than that of the free metal. Extraction of the metal from its ore involves reduction of the
oxidized form to free metal, resulting in an increase in internal free energy. Consequently the metal
will try to lose its excess energy by becoming oxidized again, through loss of electrons. This oxidizing
tendency of a metal is the driving force for corrosion and it is found in virtually all metals except the
very noble metals such as gold or platinum.

extraction corrosion
ORE METAL CORROSION
(reduction- (oxidation- PRODUCTION
gain of elec- loss of elec-
trons) trons)
Stable Metastable Stable

2.2. General classification

Corrosion is generally classified as wet or dry. In the former a corroding metal or alloy is in contact
with an aqueous or organic liquid. In many practical situations the corroding liquid can also contain
aggressive ions such as Cl- , SO4-- , etc.... which may accelerate the rate of corrosion. In the case of dry
corrosion the environment is gaseous and often both high temperatures and reactive gases are involved.

In the case of wet corrosion (also called electro-chemical corrosion) the electrochemical reaction
which is responsible for damage during corrosion is:
e. g . iron

Felattice Feaq ++ + 2e- ( 2.1.)

Atmospheric corrosion may be considered as a special type of wet corrosion since the corrosion
processes evolve in a wet film on the metal surface formed by condensation from the atmosphere

For dry corrosion (also called chemical corrosion or high temperature oxidation ) the corrosion
reaction is
e.g. iron :

Felattice Feoxyde++ + 2e- (2.2.)

Wet corrosion is the most common type of corrosion. Therefore we will only consider this kind of
corrosion in the rest of this paper.
2.3. Corrosion process : anodic and cathodic half cell reactions

Suppose that a metal rod (M) is placed in an aqueous solution. An equilibrium is soon set up between
the solution, the metal (M) and its ions (Mn+) in the solution :

M Mn+ + n e- (2.3.)

This is illustrated in fig. 2.1. For each ion sent into the solution, n electrons remain in the metal. The
metal rod is thus negatively charged. This negatively charge would quickly attract the positive ions
(Mn+), if the conditions deviated from the equilibrium conditions. Thus, the reaction from left to right

METAL

M n+
M
atom ion

ne ELECTROLYTE
Electrons

METAL
METAL METAL

M e +
M M
M e + e +
M M
M M e +
M
M +
e M e +
M

(i) (ii) (iii)

Immediately on immersion Transient state Dynamic equilibrium

Fig. 2.1. Schematic corrosion reaction

stops rapidly because otherwise the metal rod acquires too much electrical charge. Therefore : metals
do not dissolve when the metal cannot get rid or the electrons left in it. This is an important conclusion.
In other words the oxidation reaction (which takes place at the anodic areas or sites of the rod anodic
half cell) of the metal M

M Mn+ + n e- (2.4.)

cannot go on if there isn't a reduction reaction (cathodic half cell reaction) which consumes the
liberated electrons.

There are two cathodic reactions of particular importance to aqueous corrosion :

In neutral or alkaline solutions, oxygen is reduced to hydroxyl anions

O2 + 2H2O + 4e-_ 4 OH- (2.5.)

2 Version 0.1 W. Bogaerts & J. Zheng