Module4(8 of 12)

Corrosion: Introduction, Causes, consequences, Mechanism, Laws of Dry

Corrosion, Wet Corrosion , Factors Influencing Corrosion, Protective measures
against corrosion.]

Introduction & Definition:

• Corrosion is an undesired chemical or electrochemical phenomenon and

involves gradual loss of metal by the action of its environment.

• When a metal is exposed to a certain gaseous or liquid environment, its

surface gradually undergoes a chemical or electrochemical reaction with the
environment and gets deteriorated after some time.

• Rusting of Iron is most common example of corrosion. When a piece of iron

is exposed to the atmosphere, a reddish brown coating is deposited on its
surface by the combined action of air, water and CO2 and metal is slowly
eaten away.

• Corrosion starts from the surface of metal and involves a gradual loss of the
metal and involves a gradual loss of the metal. All metals and alloys are
susceptible (sensitive) to corrosion in one or the other environment. The
extent of corrosion depends upon the nature of metal and the nature of
environment.

• Even the gold which is highly resistant to corrosion under ordinary

conditions gets readily corrodes when exposed to an atmosphere of mercury.

• Although corrosion is a slow process, yet the losses caused by it are

substantial and sometimes heavy also. It involves the destruction of
machines and equipments and sometimes may lead to shutdown of plants.

Therefore, we must be familiar with this gigantic problem and should

thoroughly understand the causes and mechanism of its occurance.

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 Thus corrosion may defined as –

“The gradual disintegradation or deterioration of a metal by a chemical or

electrochemical action of its environment is called corrosion”

Causes of corrosion

Most of the metals occur in nature in the combined state, usually in the form of
oxides, sulphides, sulphates, carbonates etc. Only a few noble metals Like Au, Pt
etc occur in nature in the elemental state. The form in which a metal occurs in
nature is its thermodynamically stable state and corresponds to low energy of state
of the system.

The process used for the extraction of metal from its ores involves the consumption
of lot of energy. Therefore, the pure metal obtained from an ore is associated with
some extra amount of energy as compared to the form in which it occurred in
nature. Consequently it is present in lesser stable thermodynamic state, and has
tendency to return back to its natural thermodynamic state which is more stable.
Since corrosion involves the formation of a stable compound, metals have a natural
tendency to get corroded under suitable sets of conditions.

The metals like Au, Pt etc which occur in the elemental state in nature are already
in their stable thermodynamic state and are much less susceptible to corrosion
under ordinary conditions.

Consequences of Corrosion:

Although corrosion is a slow process, yet the losses caused by it are substantial and
sometimes heavy also.

Some of the important economic and social consequences of corrosion are as

follows:

• Corrosion involves the gradual eating of metals and therefore it leads to the
deterioration of machines and equipments. This reduces their efficiency. It
may also lead to the failure of machine and consequently the shutdown of
the plants.

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 • Economic consequence: Rusting is serious economic problem, and it has
been estimated that approximately 15% of the total annual production of
iron is mainly use to replace the iron rendered useless by rusting.

• The cost involve in adopting the preventive measures to check corrosion are
substantial. The repairing and replacement of corroded parts are also quite
expensive. This adds to the cost of production and consequently the cost of
production is higher.

• On account of corrosion, the products obtained may be contaminated and

may lead to several problem including health hazards.

• Corrosion may also pose problems to the safe operation of the plant. It may
lead to an explosion, collapse of construction due to sudden failure or fire
hazard.

• Corrosion may also create pollution problem due to escaping harmful

corrosion products from the corroded machine into the atmosphere.

This corrosion is highly undesirable as it leads to several economic and

social problems.

Types and Mechanism of Corrosion:

1. Dry Corrosion (Chemical Corrosion)

2. Wet Corrosion (Electrochemical Corrosion)

Dry Corrosion (Chemical Corrosion)

The action caused by direct chemical action of atmosphere or environmental gases

(such as O2, SO2, H2S, halogen etc) or anhydrous liquids on metal surfaces is
called chemical corrosion or dry corrosion.
The important types of dry corrosion are as follows –
(i) Oxidation corrosion
(ii) Corrosion by gases
(iii) Liquid metal corrosion

(i) Oxidation corrosion

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The oxidation corrosion occurs through the direct action of oxygen on metals,
usually in the absence of moisture. This type of corrosion may occur even at
ordinary temperatures. For examples- alkali metals (Li, Na, K etc) and alkali earth
metals (Be, Mg, Ca etc) get oxidized even at ordinary temperatures and get
corroded. Most of the other metal gets oxidized at high temperature.
Mechanism:
When a metal is exposed to air, absorption of oxygen takes place even at ordinary
temperatures. This absorption is purely physical in nature and is due to
Vanderwaal’s forces. However due to climatic changes, the absorbed oxygen may
gradually enter into chemical combination with the metal by electron transfer
between the metal atoms and oxygen as shown below---

On account of the above electron transfer reactions, a metal oxide scale is formed
at the metal surface. This scales acts as a barrier and tends to prevent the
underlying metal atoms to come in contact with oxygen. Further oxidation can take
place only when either the underlying metal gets diffused outwards through the
scales to the surface or oxygen gets penetrated inwards through the scales.

In fact, both the processes take place simultaneously but the outward diffusion of
metal is faster as compared to the inward diffusion of oxygen because metal ions
being smaller than oxygen ions possess high mobility. Thus, once the metal surface
is covered with a monolayer of oxide film, the growth of the oxide film takes place
perpendicular to the metal surface and this result in the formation of thick oxide
film.

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The nature of oxide film formed on the metal surface plays an important role in
oxidation corrosion, as is clear from following discussion.
(a) When the oxide film is stable e.g. Al, Sn, Pb, Cu
(b) When the oxide film is unstable e.g. Ag, Au, Pt
(c) When the oxide film is volatile e.g. Molybdenum (MoO3)
(d) When the oxide film is porous e.g. Alkali metals & Alkaline earth metal
(a) When the oxide film is stable: It cuts off the penetration of oxygen to the
underlying metal and acts as protective coating. Such a film prevents the further
corrosion of metal. The film formed in the oxidation corrosion of Al, Sn, Pb, Cu
etc are this type.

(b) When the oxide film is unstable : It decomposes back into the metal and
oxygen.
Metal Oxide Metal + Oxygen
In such case, oxidation corrosion is not possible. Such films are formed in the
cases of Ag, Au, Pt etc. This is why these metal donot undergo oxidation
corrosion.

(c) When the oxide film is volatile: Oxide film volatilizes as soon as it is formed,
the underlying metal gets exposed to the further attack. This causes rapid and
continuous corrosion. Such film s formed in the case of Molybdenum (MoO3 is
volatile)

(d) When the oxide film is porous:

When the oxide film is porous, the atmospheric oxygen can penetrate inward easily
and can attack the underlying metal. Hence the corrosion will continue
unobstructed till the entire metal gets completely converted into its oxide. Such
films are formed by alkali metals and alkaline earth metals.

This can be explained on the basis of Pilling –Bed worth ratio.

Pilling –Bed worth ratio: The ratio of the volume of oxide formed to the volume
of metal consumed is called Pilling-Bed worth ratio.
In case of alkali metals and alkaline earth metals, the volume of oxide film formed
on the surface is much less as that of the metal consumed. Consequently the oxide
film develops cracks and pores and allows free access of oxygen to the underlying
metal. On the other hand, in case of metals such as Pb, Sn, Al etc the volume of
the oxide film formed on the metal surface is greater than that of the metal

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consumed. Hence, the oxide layer is non-porous and protects the underlying metal
from further oxidation.
(ii) Corrosion by gases:
Several gases such as SO2 , H2S, Cl2 , F2 etc also cause corrosion of metals. The
extent to which a gas corrodes a metal depends upon the chemical affinity of the
gas for the metal. In such case, the degree of attack depends upon whether the film
formed is porous or nonporous. When the film formed on the metal surface is
porous, it allows the penetration of the gas to the underlying metal and the entire
metal gets spoiled. e.g. corrosion of steel by H2S, Corrosion of tin by Chlorine.
On the other hand, when the film formed on the metal surface is non-porous, it
restrict the penetration of the gas and protects the underlying metal. Thus, the
intensity of corrosion decreases. e.g. corrosion of silver by chlorine
Corrosion by Hydrogen: When a metal is exposed to hydrogen environment,
hydrogen diffuses into the metal lattice in the form of atoms and collects in the
interstitial spaces present in the lattice. Further diffusion helps hydrogen atoms to
combine together to form H2gas. This develops pressure inside the lattice and
causes cracking or blistering of metals.

(iii) Liquid metal corrosion:

When a liquid metal is made to flow at high temperatures over a solid metal or
alloys, the solid metal or alloy usually gets weakened. This type of corrosion is
called liquid metal corrosion and is common in nuclear energy devices. The liquid
metal corrosion is due to the dissolution of the solid metal by the following liquid
metal or by the internal penetration of the liquid metal into the solid metal.

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