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MODULE 3

CORROSION
and its Types
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.

Corrosion is a surface
phenomenon.
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 two main types of dry corrosion;

1. Oxidation corrosion (or) corrosion by oxygen


2. Corrosion by hydrogen.
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.
Example: Iron, alkaline-earth metals
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 oxide
D - density of the metal
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 Fe, 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, Sn, Pb, 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
CORROSION BY HYDROGEN

(a) HYDROGEN EMBRITTLEMENT:


Contact of metal with H2S results in the generation of
atomic hydrogen
E.g. Fe + H2S → FeS + 2H
H + H → H2 ↑

Corrosion caused by the exposure of metal to hydrogen


environment.
Hydrogen in atomic state diffuses into the metal matrix
and collects in the voids present in the metal.
The hydrogen atoms combine to form H2 gas.
A very high pressure is developed, which results in cracks
and blisters on metal. This process is called hydrogen
embrittlement.
(b) DECARBURISATION
At higher temperature atomic hydrogen is
formed by the thermal dissociation of molecular
hydrogen.
H2 → 2H
When steel is exposed to this environment, the
atomic hydrogen readily combines with carbon
of steel and produces methane gas.
C + 4H → CH4↑
Collection of these gases in the voids develop
very high pressure, which causes cracking.
Thus the process of decreases in carbon content
in steel is termed as “Decarburisation” of steel.
WET (or) ELECTRO-CHEMICAL
CORROSION

Wet corrosion occurs under the following 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 20