MODULE 3 for CAT 2

CORROSION
and its Types
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- 5
Examples for differential aeration
corrosion

 Pitting or localized corrosion

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

6
(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. 8
 (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,
therefore gets corroded easily.
Stress Corrosion/Cracking
• Combined effect of tensile stress and
corrosive environment
• Ex : Cu in Ammonia solution, mild steel in
Strong nitrate, caustic alkalis.
• Stress is caused due to heavy working like
rolling, drawing or insufficient annealing.
• It occurs along narrow paths and not on
the surface.
• The presence of stress produces strains
thus resulting in localized zones of high
electrode potential. 12
12
 Season cracking : Copper alloys mainly brasses
undergoes seasonal corrosion.
• Pure copper is free from corrosion.
• Copper with small amounts of P, As, Al, Zn show
marked sensitivity.
• Alpha Brass (highly stressed 75%Cu + 25% Zn)
undergoes intergranular cracking in the presence
of ammonia.
• Grain boundaries are anodic.
• Cu and Zn form stable complex with ammonia.
Dissolution of brass takes place. Formation of
cracks occurs.
13
13
Standard Potentials at Electrode Reactions at 25 0C

14
 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.

18
 (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.
19
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 20

may become active

(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.

21
(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, Pb, Zn (Amphoteric
Metals) dissolves in alkaline medium.

22
 (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.
23