Chapter II

CORROSION
and its CONTROL
CORROSION AND ITS
CONTROL

DEFINITION
Corrosion is defined as the gradual
destruction or deterioration of
metals or alloys by the chemical or
electrochemical reaction with its
environment.
 CONSEQUENCES OF CORROSION

Due to formation of corrosion product over the

machinery, the efficiency of the machine gets lost.

The products gets contaminated due to corrosion.

The corroded equipment must be replaced frequently.

Plant gets failure due to corrosion.

Corrosion releases toxic products, health hazard, etc.

 CLASSIFICATION OF CORROSION
Based on the environment, corrosion is classified in to
1. Dry or Chemical corrosion
2. Wet or Electrochemical corrosion.

Dry or Chemical corrosion:

Dry corrosion is due to the attack of metal surfaces by
the atmospheric gases such as oxygen, hydrogen
sulphide, sulphur dioxide, nitrogen, inorganic liquids
etc.

There are three main types of dry corrosion;

1. Oxidation corrosion (or) corrosion by oxygen

2. Corrosion by hydrogen.
3. Liquid – metal corrosion.
 OXIDATION CORROSION

 Oxidation corrosion is brought about by the direct

attack of oxygen at low or high temperatures on
metal surface in the absence of moisture.
 Alkali metals like (Li, Na, K, etc) and alkaline-earth
metals (Mg, Ca, Sr, etc) are rapidly oxidised at low
tempt.
 At high temperature, almost all metals (expect Ag,
Au and Pt) are oxidized.
 MECHANISM OF DRY CORROSION

Oxidation occurs first at the surface of the metal

resulting in the formation of metal ions (M2+), which
occurs at the metal/oxide interface.
M → M2+ +2e-

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Oxygen changes to ionic form (O2-) due to the
transfer of electron from metal, which
occurs at the oxide film / environment
interface.
½ O2 + 2e- → O2-

Oxide ions reacts with the metal ion to form

the metal- oxide film.

M + ½ O2 → M2+ +O2- ≡ MO (Metal-oxide film)

 NATURE OF OXIDE FILM

The nature of oxide film formed on the metal surface plays in

important role in oxidation corrosion.

(i) STABLE OXIDE LAYER

A stable oxide layer behaves as a protective

coating and no further corrosion can develop.
Example: oxides of Al, Sn, Pb, Cu, etc., are stable oxide layers.

(ii) UNSTABLE OXIDE LAYER

Unstable oxide layer is mainly produced on the surface of

noble metals, which decomposes back in to the metal and
oxygen.
Metal oxide → Metal +Oxygen

Example: Oxides of Pt, Ag, etc., are unstable oxide layers.

(iii) VOLATILE OXIDE LAYER
The oxide layer volatilizes as soon as it is
formed, leaving the metal surface for further
corrosion.

Example: Molybdenum oxide is volatile.

(iv) POROUS OXIDE LAYER

Metal oxides having pores and cracks allow
penetration of oxygen to the underlying
metal, resulting in the complete conversion
of metal into its oxide.
 PILLING –BEDWORTH RATIO

• The ratio of the volume of the oxide formed to

the volume of the metal consumed is called
“pilling-bedworth ratio”.

R = Md/nmD

Where M - mass of metal oxide

m - atomic weight
d - density of the metal
D - density of the scale
n- number of metal atoms in a formula of the scale
(PILLING-BEDWORTH RULE)

According to Pilling–Bedworth rule,

1. If the volume of the oxide layer formed is less than the

volume of the metal, the oxide layer is porous and non-
protective.
Example: Oxides of alkali and alkaline earth metals.

2. If the volume of the oxide layer formed is greater than the

volume of the metal, the oxide layer is subjected to cracking
and spalling resulting in poor oxidation resistance and
protection.
Example: Oxides of heavy metals such as Sb,V, W, etc.

3. If the volume of oxide layer is equal to the volume of the

metal then there will be protective oxide film formation.
Example: Oxides of Al, Pb, Ni, etc.
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 CORROSION BY OTHER GASES

 Gases like SO2, CO2, Cl2, H2S etc – induce corrosion

action on metals
 Corrosion effect depends on the chemical affinity
between the metal and the gas.
 The degree of attack by gases depends on the formation
of protective or non-protective films on the metal
surface.
(1) If the film is non-porous or protective, the intensity of
attack decreases. Eg. AgCl film – attack of Cl2 on Ag
(2) If the film is porous or non-protective, the surface of the
whole metal is gradually destroyed.
Eg. Dry Cl2 gas attack on Sn – formation of volatile SnCl4
– fresh surface is exposed for further attack 12
 WET (or) ELECTRO-CHEMICAL
CORROSION

Wet corrosion occurs under the foll. conditions,

 When two dissimilar metals are in contact with each

other in the presence of an aqueous solution or
moisture.

 When two dissimilar parts of the same metal are in

contact with an aqueous solution of an electrolyte.
 MECHANISM OF WET CORROSION
According to electrochemical theory of corrosion,
the wet corrosion involves two steps.
a) Oxidation or metal dissolution
b) Reduction

Metal dissolution occurs always at anode leading to

the formation of metal ions and electrons
M → Mn+ + ne-

At cathode, electron consumption resulting in either

evolution of hydrogen or absorption of oxygen
depending on the nature of corrosion environment.
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(a) Acidic environment

If the corrosive environment is acidic, hydrogen evolution

occurs at cathodic part.

2H+ + 2e- → H2↑

(b) Alkaline or Neutral environment

If the corrosive environment is slightly alkaline (or) neutral,

hydroxide ion forms at cathodic part.

½ O2 + 2e- +H2O → 2OH-

Thus the metal ions (from anodic part) and non-metallic ions
(from cathodic part ) diffuse towards each other through
conduction medium and form a corrosion product between
anode and cathode.
 a) Hydrogen evolution type corrosion
 Metals have negative reduction potential
i.e., below hydrogen reduction potential
value in the electrochemical series get
dissolved in acidic solution with
simultaneous liberation of “hydrogen gas”.
 Example: Iron metal in contact with non-
oxidizing acid like HCl results in H2
evolution
 At anode: Iron (Fe) undergoes dissolution to
Fe2+ with the liberation of electrons.
 At cathode: The liberated electrons follow
from anode to cathode, where H+ ions get
reduced to H2.
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 b) Absorption of oxygen or formation of hydroxide
ion type corrosion
 Fe surface usually contains a coating of Iron oxide and if
this oxide layer develops, cracking happens.
 As a result anodic areas are created on the surface and
remaining area acts as cathode.
 Example: Iron metal in contact with a neutral solution of
electrolyte in the presence of O2, OH- ions are formed.
 At anode: Iron (Fe) undergoes dissolution to Fe2+ with the
liberation of electrons.
 At cathode: The liberated electrons follow from anode to
cathode, where dissolved O2 is consumed to form OH-
ions.
1/2O2 + H2O + 2e- 2OH-
Fe2+ + 2OH- Fe(OH)2
Fe(OH)2 + 2H2O + O2 4Fe(OH)3 (rust)
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 Chemical Corrosion Electrochemical Corrosion
It occurs only in dry condition It occurs in the presence of
moisture or electrolyte
It is due to the direct chemical It is due to the set up of a
attack of the metal by the large number of cathodic and
environment anodic areas
Even a homogeneous metal Hetergeneous surface or
surface gets corroded bimetallic contact is required
for corrosion
Corrosion products Corrosion occurs at the anode,
accumulate in the same place, while products formed
where corrosion occurs. elsewhere
Chemical corrosion is self- It is continuous process
controlled
It follows adsorption It follows electrochemical
mechanism reaction
Eg. Formation of mild scale on Eg. Rusting of iron in moist
iron surface atmosphere 18
TYPES OF ELECTROCHEMICAL CORROSION

GALVANIC CORROSION

When two different metals are in contact with each

other in the presence of an aqueous solution or moisture,
galvanic corrosion occurs. Here, the more active metal
(with more negative electrode potential) acts as anode and
the less active metal (with less negative potential) acts as
cathode.

Example for galvanic corrosion

Steel screw in a brass marine hardware corrodes. This is
due to galvanic corrosion. Iron (higher position in
electrochemical series) because anodic and is attacked
and corroded, while brass (lower in electrochemical series)
acts as cathodic and is not attacked.
Bolt and nut made of the same metal is preferred.
Why?
It is preferred in practice, because galvanic
corrosion is avoided due to homogeneous metals (no
anodic and cathodic part).

Prevention:
 Avoid unfavorable area effect
 Selection of metals & alloys
 Insulating dissimilar metals
 Using inhibitors
 Applying cathodic protection
 DIFFERENTIAL AERATION CORROSION

This type of corrosion occurs when a metal is

exposed to varying concentration of oxygen or any
electrolyte on the surface of the base metal.

Example

• Metals partially immersed in water (or) conducting

solution (called water line corrosion).

• If a metal is partially immersed in a conducting

solution the metal part above the solution is more
aerated and hence become cathodic.

• On the other hand, the metal part inside the

solution is less aerated and thus, become anodic
and suffers corrosion.
At anode (less aerated) corrosion occurs
M → M2+ +2e-
At cathode (more aerated part) OH- ions are produced
½ O2 +H2O + 2e- → 2 OH- 22
Examples for differential aeration
corrosion

 Pitting or localized corrosion

 Crevice corrosion
 Soil corrosion
 Fencing Corrosion
 Waterline Corrosion

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(a) Pitting Corrosion

This is a localised attack, resulting in the formation

of a hole around which the metal is relatively
unattacked.

Example
Metal area covered by a drop of water, sand, dust,
scale etc.,

• Consider a drop of water or aqueous NaCl resting

on a metal surface.

• The area covered by the drop of H2O acts as an

anode due to less O2 conc., and suffers corrosion.

• The uncovered area (freely exposed to air) acts as a

cathode due to high oxygen concentration
The rate of corrosion will be more, when the area of
cathode is larger and the area of anode is smaller. A small
hole or pit is formed on the surface of the metal.

At anode
Iron is oxidized to Fe2+ ions (Fe → Fe2+ +2e-)

At cathode
Oxygen is converted to OH- ions. (1/2O2 +H2O +2e- → 2OH-)

Net reaction is
Fe2+ +2OH- → Fe(OH)2 →Fe(OH)3
This type of corrosion is called pitting. 25
 (b) Crevice corrosion

• If a crevice between different metallic objects or

between metal and non-metallic material is in
contact with liquids, the crevice becomes the
anodic region and suffers corrosion.
• This is due to less oxygen with crevice area.
• The exposed areas act as the cathode.
 (c) PIPELINE CORROSION
• Differential aeration corrosion may also
occur in different parts of pipeline.
• Buried pipelines or cables passing from one
type of soil to another, example from clay
(less aerated) to sand (more aerated) may get
corroded due to differential aeration.
 (d) CORROSION ON WIRE-FENCE
• A wire fence in which the areas where the wires cross are
less aerated than the rest of the fence and hence corrosion
occurs at the wire crossings, which are anodic.

Other examples for differential aeration corrosion

(i) Corrosion occurring under metal washers, where oxygen
cannot diffuse easily.

(ii) Lead pipeline passing through clay to cinders undergo

corrosion. Since the pipeline under cinders is more aerated,
it gets corroded easily.
 FACTORS INFLUENCING CORROSION
The rate and extent of corrosion depends
mainly on
i. Nature of the metal
ii. Nature of the environment

Nature of the metal

A) Position in EMF series

 The extent of corrosion depends upon the

position of the metal in the EMF series.
 Greater the oxidation potential, greater is the
rate of corrosion.
 When two metals are in electrical contact, the
metal higher (-) ve electrode potential in the EMF
series becomes anodic and suffers corrosion.
 Further, the rate and severity of corrosion
depends upon the difference in their positions in
the EMF series.
 Greater the difference, faster is the corrosion of
anodic metal.

(b) Relative areas of the anode & cathode

 The rate of corrosion is more when area of the
cathode is larger.
 When cathodic area is larger, the demand for
electrons will be more and this results in an
increased rate of dissolution of metals at anodic
regions.
(c) Purity of the metal
 The 100% pure metal will not undergo any type
of corrosion.
 But, the presence of impurities in a metal
create heterogeneity and thus galvanic cells are
sets up with distinct anodic and cathodic area
in the metal.
 Higher the percentage of impurity, faster is the
rate of corrosion of the anodic metal.

(d) Physical state of the metal

 Metal components subjected to unevenly
distributed stresses are easily corroded.
 Even in a pure metal, the areas under stress
tend to be anodic and suffer corrosion.
(e) Nature of the Corrosion Product

 If the corrosion product is soluble in the

corroding medium, the corrosion of the
metal will proceed faster.

 On the other hand, if the corrosion

product is insoluble, then the protective
film formed will tend to suppress corrosion.

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 (f) Nature of the oxide film
 Metals such as Mg, Ca, Ba, etc., form oxides
whose volume is less than the volume of the
metal.
 Hence, the oxide film formed will be
porous, through which oxygen can diffuse
and bring about further corrosion.
 On the other hand metals like Al, Cr, Ni
etc. form oxides whose volume is greater
and the non-porous oxide film so formed
will protect the metal from further
corrosion.
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 NATURE OF THE ENVIRONMENT
(A) Temperature
 The rate of chemical reaction and the rate
of diffusion of ions increases with rise in
temperature
 Hence, corrosion increases with
temperature.
 A passive metal may become active at a
higher temperature.

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(B) Humidity
The rate of corrosion will be more, when
the humidity in the environment is high.
The moisture acts as a solvent for the
oxygen in the air to produce the
electrolyte, which is essential for setting
up a corrosion cell.
Rusting of iron increases when the
relative humidity of air reaches from
60 to 80 percent.

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(C) Effect of pH

The rate of corrosion is maximum when

the corrosive environment is acidic.
In general, acidic environment is more
corrosive than alkaline or neutral medium.
Corrosion rate can be reduced by
increasing the pH of the medium.
But metals such as Al, Zn dissolves in
alkaline medium.

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 (D) NATURE OF THE ELECTROLYTE

 If the electrolyte consists of silicate ions,

they form insoluble silicates and prevent
further corrosion.

 On the other hand if chloride ions present,

they destroy the protective film and the
surface is exposed for further corrosion.

 If the conductance of electrolyte is more,

the corrosion current is easily conducted
and hence the rate of corrosion is
increased.
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(E) Conductance of the corroding medium
The corrosion current depends upon the
internal resistance of the short circuited
cells, which in turn depends on the
conductance of the electrolytic medium.
If the conductance of the soil is more, the
corrosion of underground structure will
also be more.
Conductance in clayey, soils and
mineralized soils is more.

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