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Corrosion & its Control

Factors Influencing Corrosion Galvanic series:


EMF series does not account for
Extent of Corrosion depends mainly on, the Corrosion of all metals &
alloys. So, a more practical
 Nature of the metal
series, called galvanic series is
 Nature of the environment prepared.

Nature of the metal Anodic

Position in the galvanic series:


Extent of corrosion depends upon
the position of the metal in the
galvanic series.

Greater the oxidation potential,


greater is the rate of corrosion.

When two metals are in direct


contact, the metal higher up in
the galvanic series becomes
anodic and suffers corrosion.
Cathodic
Factors Influencing Corrosion
Relative areas of the anode and cathode:
Rate of corrosion is more if the size of cathodic area is large

Large Cathode
(Steel) Small Anode
(Aluminium)

e-n flow

If cathodic area is larger, the demand for electrons will be more and
this results in the increase of rate of oxidation of metal at anode. i.e,
high rate of corrosion at anode.
Factors Influencing Corrosion
Purity of the metal:
Impurities present in a metal create heterogeneity and thus
galvanic cells are set up with distinct anodic and cathodic areas in
the metal.

Higher the percentage of impurity present in a metal, faster is the


rate of corrosion of the anodic metal.

Eg:- Impurities like Pb, Fe, etc. in Zn lead to the formation of tiny
electrochemical cells at the exposed part of the impurity and the
corrosion of Zn around the impurity takes place.
Factors Influencing Corrosion
Physical state of the metal:

Metallic materials with unevenly


distributed stresses are easily
corroded.

Even in a pure metal, the areas


under stress acts as anode and get
corroded. Caustic embrittlement
takes place in stressed parts such as
bends, joints, rivets, etc. in boilers.

Caustic embrittlement takes place in


stressed parts such as bends, joints,
rivets, etc. in boilers.
Factors Influencing Corrosion
Nature of the oxide film:

Piling Bed-Worth Rule

If, Volume of Oxide < Volume of metal

Oxide film is porous and non-protective


CORROSION CONTINUES due to penetration of O2 through pores
Eg:- Metals such as Mg, Ca, Ba, etc.

If, Volume of Oxide > Volume of metal

Oxide film is non-porous and protective


NO FURTHER CORROSION
Eg:- Metals such as Al, Cr, Ni, etc.
Factors Influencing Corrosion

Nature of the Environment

Temperature:

Corrosion increases with temperature due to the increase in rate of


diffusion of ions

Humidity :

Atmospheric corrosion of Fe is slow in


dry air but the rate of corrosion increases
rapidly in presence of moisture. This is
due to the fact that moisture acts as a
solvent for the oxygen in the air to form
electrolyte and setting up an
electrochemical cell.

Example: rusting of iron increases when


the moisture content increases from
60% to 80%.
Factors Influencing Corrosion
Effect of pH :
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.
Factors Influencing Corrosion
Nature of the electrolyte :
If the electrolyte consists of silicate ions, they form insoluble
silicates (that acts as protective coating) and prevent further
corrosion.

If the electrolyte consists of chloride ions, they destroy the


protective film and the surface is exposed for further corrosion.

If the conductance of electrolyte is high then, the corrosion


current is easily conducted and hence the rate of corrosion is
increased.
Factors Influencing Corrosion
Concentration of O2 and formation of O2 concentration cells:

Rate of corrosion increases


with increasing supply of
oxygen.

Less oxygenated part of


the metal acts as anode
and more oxygenated part
of metal acts as cathode.
Factors Influencing Corrosion
Differential aeration:

Due to differential aeration,


Corrosion often takes place
under,
metal washers
buried pipelines
cables passing through different
types of soil

Eg:- Lead pipelines passing


through clay and sand. Pipeline
buried under clay get corroded
easily because clay is less
aerated than sand.
Corrosion Control Ornaments

Corrosion can be controlled by two methods,

By modifying the metal


By modifying the environment

Corrosion control by modifying the metal

Selection of the metal:


Selection of right type of metal is the
main factor for corrosion control.

Eg:- Noble metals that are immune to Surgical Instruments


corrosion are used for producing
ornaments and surgical instruments.
Corrosion Control
Using pure metal:

Presence of impurities in a metal cause heterogeneity and


decreases the corrosion–resistance of the metal.

Eg:- Presence of just 0.02% of iron in aluminium decreases its


corrosion resistance.

Using metal alloys:

Corrosion resistance can be improved by alloying the metal


with suitable metal.

Eg:- Presence of chromium in stainless steel produces a


protective oxide film.
Corrosion Control
Metallic materials should be designed in such a way to resist corrosion

Iron
Important Design Principles:
Stainless steel
The contact of two bolt & nut
dissimilar metals in the
presence of the corroding
solution should always be Iron
avoided, otherwise the
more active metal will act
as anode and corrosion
will be localized.
Corrosion Control

Important Design Principles:

If the contact between two dissimilar metals is unavoidable two


metals are chosen in such a way that the anodic metal should be
as large as possible and cathodic metal should be as small as
possible.
Large Anode
(Aluminium)

Large Cathode Small Anode


(Aluminium) Small Cathode
(Steel) (Steel)

e-n flow
e-n flow

Severe Corrosion Negligible Corrosion


Corrosion Control

Important Design Principles:


The (contacting) two dissimilar metals should possess close
positions in the EMF series.
If direct contact is not possible to avoid, the metals can be
insulated well before connecting to avoid the direct electric contact
of metals.
Corrosion Control

Important Design Principles:


The anodic metal should be used without any paint coatings for
connecting with cathodic metal. Because even a slight break in
paint coating will lead to localized corrosion.

On joining different metals, welded joints should be used instead of


riveted joints.
Corrosion Control

Important Design Principles:

The design should provide easy cleaning and flushing of the


corner and bends in the metallic equipment.

i.e., Sharp corners and recess should be avoided.


Corrosion Control
Important Design Principles:

Stagnant water is avoided


Avoid angles and pockets in which by providing drain holes
water can collect.

The risk of dirt build-up is reduced Instead, use a shape that


with radiused corners. promotes draining
Corrosion Control

Important Design Principles:

Metallic equipments should be supported on legs to permit


air circulation and to avoid the formation of damp areas
under the equipment.
Corrosion Control
Cathodic Protection:
Principle: Corroding anode is forcibly converted into cathode.
Types:
1. Sacrificial anodic protection
2. Impressed current cathodic
protection
Sacrificial anodic protection method

metallic equipment to be protected is electrically


connected to more active anodic metal
SACRIFICIAL ANODE
Ship Without Sacrificial anode

Initially Then..

At Seashore… Finally
RUSTY SHIP
RUSTY SHIP WRECK
RUSTY ANCHORS
Corrosion Control
Impressed current cathodic protection:
(+ ) (– )
DC

B a c k fill
B u rie d p ip e

G r a p h ite a n o d e S o il

current is applied (from a battery) in


opposite direction to nullify the
corrosion current
Corrosion Control Impressed current cathodic protection:
Corrosion Control

Corrosion control by modifying the environment

Corrosion Inhibitors:
Substance which on addition in small quantities to the corrosive
environment reduces the corrosion of metal is called inhibitors.

Types of Inhibitors: 1. Anodic inhibitors


2. Cathodic inhibitors

Anodic inhibitors:
Chemicals like chromates, phosphates, tungstates, when added to
corrosive environment produces sparingly soluble compounds by
reacting with metal ions (produced because of corrosion).

The sparingly soluble compounds get absorbed on the metal surface


forms a protective film and thereby reduces corrosion rate.

This type of corrosion control is not fully reliable because, certain


areas of metal are not covered by the film and this leads to severe
corrosion.
Corrosion Control
Cathodic inhibitors:

In acidic solution, the main cathodic reaction is liberation of H 2.


+ -
2
H2
(a
)
q +
e���
H
(g
2)
In an acidic solution, the corrosion can be controlled by slowing
down the diffusion of H+ ions through the cathode.This can be done
by adding organic inhibitors like amines, pyridine, etc. They absorb
over the cathodic metal surface and act as a protective layer.

In a neutral solution, the cathodic reaction is,


1 - -
H
O
2+O+�
22e �

2
OH
2
The formation of ions is only due to the presence of oxygen. By
eliminating the oxygen from the medium, the corrosion rate can be
reduced. Oxygen can be removed by adding some reducing agents
like Na2SO3 or by deaeration.
Corrosion Control

Application of protective coatings:

Metallic surface can be


protected from corrosion by
covering it by organic or
inorganic coating.
Corrosion Control

Deaeration

Presence of more O2 is
harmful and it increases the
corrosion rate. Dissolved
oxygen can be removed by
deaeration using mechanical
agitation.

mechanical agitator
Corrosion Control

Deactivation
Removal of oxygen can be attained also by adding chemicals like
Na2SO3, hydrazine etc.,

2
N
a
2S
O
3+
O
2�

�2
N
a
2S
O
4

N
H
2
4+�
O
2�
�N
+
22
HO
2
Corrosion Control

Dehumidification

In this method, moisture from the air


is removed by lowering the relative
humidity of the surrounding air.

This can be achieved by adding silica


gel which can absorb moisture.