CORROSION AND ITS CONTROL

▣ INTRODUCTION

▣ CAUSES OF CORROSION

▣ THEORIES OF CORROSION

▣ CORROSION REACTIONS

▣ TYPES OF CORROSION

▣ FACTORS EFFECTING THE CORROSION

▣ CORROSION CONTROL METHODS

 INTRODUCTION

Destruction of a metal by chemical or electrochemical reaction

with its environment.
Physical or mechanical wearing away of a metal is not called
corrosion but is called erosion
If corrosion and erosion take place together the destruction of
the metal takes place very much faster
Corrosion is an unintentional attack on a material by reaction
with a surrounding medium
The corrosion problem should be very seriously considered in
all those cases where the structure or the equipment is meant
to last many years say 20 years…
 Definition of Corrosion

Corrosion is the deterioration of materials by chemical interaction

with their environment. The term corrosion is sometimes also
applied to the degradation of plastics, concrete and wood, but
generally refers to metals.
Rusting of iron
Formation of green rust
 CAUSES OF CORROSION
The chemical combined state of the metal is known as “ore”

The ore has low energy in its thermodynamical state.

The extracted metal has high energy ,thermodynamically

unstable .

Metal converts itself into stable state by reacting with the

environment and undergoes corrosion.

The corroded metal is thermodynamically stable.

Formation of rust
Effects or disadvantages of corrosion
The valuable metallic properties like conductivity,malleability,
ductility etc are lost due to corrosion.

Life span of the metallic parts of the machineries is reduced.

The process of corrosion is very harmful and is responsible for

the enormous wastage of metal in the form of its compound.

The failure of the machinery takes place due to lose of useful

properties of metals.

The approximate estimate of loss of metal due to corrosion is

2 to 2.5 trillion dollars per annum all over the world.
 THEORIES OF CORROSION
In atmospheric corrosion the metals tend to revert to the states in
which they occur in nature.

Several theories of corrosion have been proposed from time to

time..

The three theories are

i) ACID THEORY
ii) CHEMICAL CORROSION (DRY CORROSION)
iii) ELECTROCHEMICAL CORROSION (WET
CORROSION)
 ACID THEORY
Acid theory of corrosion considers acid to be the main cause.

Rusting takes place faster in acid solutions than in neutral or basic

solutions.

Oxygen and water are necessary for rusting of iron.

This is not true for all the metals like Zn etc..

Rate of corrosion in absence of Carbon di oxide is also seen.

 Dry corrosion or chemical corrosion
The direct chemical reaction of environment/atmospheric
gases or inorganic liquids with metal surfaces .
There are three types of chemical corrosion
i) Oxidation corrosion
ii) Corrosion by other gases
iii) Liquid metal corrosion
(1.) Oxidation Corrosion: This is carried out by the direct action
of oxygen low or high temperatures on metals in absence of
moisture.
Alkali metals and Alkaline earth metals are rapidly oxidized at low
temperatures. At high temperature all metals are oxidized (except
Ag, Au, Pt).

M M2+ + 2e- (Oxidation)

O2 + 2e - 2O2- (Reduction)
M + O2 M2+ + 2O2- (Metal oxide)
Mechanism:-
1. When temp increases the metal undergoes oxidation and losses e-

2M → 2M+n + 2ne-
Metal Ion
2. Electron are gained by the oxygen molecules forms oxide ions

nO2 + 4ne- → 2n O2-

Oxide Ion
3. Scale of metal oxide formed 2M + nO2 → 2M + 2n O2
Metal Oxide
2.) Corrosion due to other gases: This type of corrosion is due
to gases like SO2, CO2, Cl2, H2S, F2 etc. In this corrosion, the
extent of corrosive effect depends mainly on the chemical affinity
between the metal and the gas involved. The degree of attack
depends on the formation of protective or non protective films on
the metal surface which is explained on the basis of Pilling
Bedworth rule.

(i) If the volume of the corrosion film formed is more than the
underlying metal, it is strongly adherent, non-porous does not
allow the penetration of corrosive gases.
Ag + Cl2 2AgCl (protective film)
(ii) If the volume of the corrosion film formed is less than the
underlying metal, it forms pores/cracks and allow the penetration
of corrosive gases leading to corrosion of the underlying metal.
Ex. In petroleum industry, H2S gas at high temperature reacts with
steel forming a FeS scale. Fe (steel) + H2S FeS (porous)

3.) Liquid metal corrosion: This corrosion is due to chemical

action of flowing liquid metal at high temperatures on solid metal
or alloy. The corrosion reaction involves either dissolution of a
solid metal by a liquid metal or internal penetration of the liquid
metal into the solid metal.
Eg. Coolant (sodium metal) leads to corrosion of cadmium in
nuclear reactors.
Wet or Electrochemical corrosion

The electrochemical corrosion occurs when

i) a conducting liquid is in contact with a metal.

ii) when two dissimilar metals or alloys are immersed

partially in the solution.

Corrosion occurs due to the presence of anodic and

cathodic areas.

At anode oxidation reactions takes place

At cathode reduction reactions takes place
Occurs when aqueous solution or liquid electrolytes are
present

Wet corrosion takes place in environments where the relative

humidity exceeds 60 %.

Wet corrosion is most efficient in waters containing salts,

such as NaCl (e.g. marine conditions), due to the high
conductivity of the solution.
Mechanism Of Electrochemical
Corrosion

Mechanism Of Electrochemical Corrosion

Anodic Reaction:
Dissolution of metal takes place.
As result metal ions are formed with the liberation of free
electrons.
M ↔ M+n + e-
Metal Ion
 Cathodic Reaction
(i) Hydrogen Evolution :- Occurs usually in acidic medium

2H+ + 2e- ↔ H2 (g)

(ii) Oxygen Absorption :- occurs when solution is aerated

sufficiently.
O2+ 4H+ + 4e- ↔ 2H2O (In acidic medium)
O2+ 4H+ + 4e- ↔ 4OH- (In basic medium)
Wet corrosion takes by the following ways.

Hydrogen gas evolution

Oxygen gas absorption

This type of corrosion occurs in acidic medium.
E.g. Considering the metal Fe, anodic reaction is dissolution of
iron as ferrous ions with liberation of electrons.
Anode: Fe---- Fe2+ + 2e- (Oxidation)

The electrons released flow through the metal from anode to

cathode, whereas H+ ions of acidic solution are eliminated as
hydrogen gas.
Cathode: 2H+ + 2e- ---- H2 (Reduction)
The overall reaction is: Fe + 2H+ ----- Fe2+ +H2

All metals above hydrogen in electrochemical series have a

tendency to get dissolved in acidic solution with simultaneous
evolution of H2 gas.
 Mechanism of wet corrosion by
hydrogen evolution
 Absorption of oxygen
Absorption of oxygen: For example, rusting of
iron in neutral aqueous solution of electrolytes
in presence of atmospheric oxygen.
Usually the surface of iron is coated with a
thin film of iron oxide.
If the film develops cracks, anodic areas are
created on the surface.
While the metal parts act as cathodes. It shows
that anodes are small areas, while the rest
metallic part forms large cathodes.
The released electrons flow from anode to
cathode through iron metal.
.
At anode: Fe ---- Fe2+ + 2e- (Oxidation)
At cathode: ½ O2 + H2O + 2e- --- 2OH- (Reduction)
Overall reaction: Fe2+ + 2OH- ----- Fe (OH)2

The product called yellow rust corresponds to

Fe2O3. 3H2O
 TYPES OF CORROSION

Different types of electrochemical corrosions are

Galvanic corrosion

Pitting corrosion

Intergrannular corrosion

Water line corrosion

 Galvanic corrosion
▣ This corrosion occurs when different metals are in contact and
exposed to corrosive atmosphere.

▣ The metal which has higher electrode potential value will form
anode and undergoes corrosion. Example: Zn-Cu galvanic
cell zinc behaves as anode and corrosion occurs, copper
behaves as cathode and protected.
 Pitting corrosion

When corrosion starts on a metal surface

at certain spots they become less open to
oxygen with the result that corrosion
proceeds faster at those very spots making
deeper and deeper cavities.
Pitting corrosion can be explained on the
basis of differential aeration.
The pit created becomes deeper, its
bottom becomes less open to oxygen
which makes it more anodic.
The part which has higher oxygen
concentration is cathodic.
Water line corrosion

The concentration of oxygen dissolved in

water is greater at the surface than deeper
down. This causes formation of a
concentration cell.

Anode is the lower portion .

Cathode is at the water level.

Due to the poor conductivity of water the

ions just below the water level are
available for reaction, the metal corrodes
just below the water level.
FACTORS EFFECTING THE CORROSION

❑ The factors that effect corrosion are

i) Nature of the metal

ii) Nature of the environment

Nature of the metal
❑ The rate and the extent of corrosion depends on the
following factors

A ) Purity of a metal
B ) Position in galvanic series
C ) Over voltage
D ) Nature of oxide film
E ) Nature of corrosion product
 Nature of the metal
1. Purity of the metal: Heterogeneity of the metal is due to the
presence of impurities which form tiny electrochemical
cells at the exposed parts. The anodic parts get corroded.

2.Electrode potentials: metals with higher reduction potentials

do not corrode easily. They are noble metals like gold,
platinum and silver. Whereas the metals with lower
reduction potentials readily undergo corrosion (e.g.. Zn,
Mg, Al etc.).

3.Position of metal in Galvanic series: Metals which possess

low reduction potentials and occupy higher end of galvanic
series undergo corrosion easily.
 When two metals are in electrical contact in presence of an
electrolyte, then the metal which is more active undergoes
corrosion.
The rate of corrosion depends on the difference in their
position in Galvanic series. Greater the difference more will be
the extent of corrosion at anode.

4.Relative areas of anodic and cathodic cells: When two

dissimilar metals or alloys are in contact, the corrosion of the
anodic part is directly proportional to the areas of the cathodic
and anodic parts. i.e, the relative areas o of corrosion is
influenced by cathodic to anodic cells.

5. Physical state of metal: Metals with small grain size have

more tendencies to undergo corrosion. Metal with more
stress/strain also undergoes corrosion easily.
6. Hydrogen over voltage: when a cathode reaction is hydrogen
evolution type, the metal with lower hydrogen over voltage on
its surface is more susceptible for corrosion, since the liberation
of hydrogen gas is easy at this condition. Hence the cathodic
reaction is very fast which in turn makes anodic reaction fast.
Hence the rate of corrosion increases. Higher the over voltage,
lesser is the corrosion.

7. Nature of surface film: If the corrosion product formed is more

stable, insoluble and non porous, it acts as protective layer and
prevents further corrosion (E.g.. Ti, Al and Cr). If the corrosion
product is porous, volatile and soluble, it further enhances the
corrosion (Fe, Zn and Mg).
 Nature of the environment
1. Temperature: the rate of corrosion reactions increases with
increase in temperature.

2. Humidity in air: the moisture or humidity present in atmosphere

furnishes water to the electrolyte which is essential for setting up
of an electrochemical cell. The oxide film formed has the tendency
to absorb moisture which creates another electrochemical cell.

3. Presence of impurities: Atmosphere is contaminated with gases

like CO2, SO2, H2S; fumes of H2SO4, HCl etc. and other suspended
particles in the vicinity of industrial areas. They are responsible for
electrical conductivity, thereby increasing corrosion.
4. pH value: pH value of the medium has the greater effect on
corrosion. Acidic pH increases the rate of corrosion.

5. Amount of oxygen in atmosphere: As the percentage of

oxygen in atmosphere increases, the rate of corrosion also
increases due to the formation of oxygen concentration cell.
The decay of metal occurs at the anodic part and the cathodic
part of the metal is protected.

6.Velocity of ions which flow in the medium: As the velocity of

the diffusion of the ions in the medium increases, the rate of
corrosion increases .
CORROSION CONTROL METHODS
The various measures taken for corrosion protection are

I) CATHODIC PROTECTION

II) SURFACE COATINGS

 CATHODIC PROTECTION
The method of protecting metals and alloys from corrosion
making them completely cathode.

To achieve this auxilary anode is provided in the corroding

medium which is connected to the structure.

Cathodic protection is of two types

i) Sacrificial anodic method

ii) Impressed current cathodic method

Cathodic Protection
Force the metal to be protected to behave like cathode.
(i) Sacrificial anodic protection:

Metal to be protected from corrosion connected to more

anodic metal
Commonly used metals Mg, Zn, Al and their alloys
Eg. A ship-hull which is made up of steel is connected to
sacrificial anode (Zn-blocks) which undergoes corrosion leaving
the base metal protected.

Eg. The underground water pipelines and water tanks are also
protected by sacrificial anode method. By referring to the
electrochemical series, the metal with low reduction potential is
connected to the base metal which acts as anode.
Impressed current method:
Direct current is applied in opposite direction to nullify the
corrosion current
Converts the corroding metal from anode to cathode.
SURFACE COATINGS
The metal surface is covered with a coating to protect it from
corrosion.
These may be
i) Metallic
ii) Organic
 METALLIC COATINGS
The metals used for coatings may be placed under two categories
i) metals which are anodic to the metal i.e., metals above it in
galvanic series.

ii) metals which are cathodic to the metal i.e., metals below it in
galvanic series.
Methods of applications of metal coatings:

Hot dipping: This technique is most widely used to control

corrosion. Hot dipping is used for producing a coating for
low melting metals such as Zn, Sn, pb ,Al.
on Iron, steel, copper which are having high melting point
usually underwent into corrosion due to their oxidising
property.
The process in general consisting of immersed a metal in a
bath of its molten coating& covered by a molten layer.
The flux cleans the base metal& prevent oxidation of metal
coating with molten solution.
Hot dipping is widely applied either by
(1)GALVANIZING (2)TINNING
 Galvanizing
It is the process in which iron or steel is protected from
corrosion by coating with a thin layer of zinc.
Iron or steel is first cleaned by pickling with dil. H2SO4
solution for 15-20 mts at 600-900c. The steel is then washed
well and dried .
Then the metal sheet is dipped in bath of molten Zinc
maintained at 4250-4300c.
The surface of bath is kept covered with a Zncl2 flux to
prevent oxide formation.
Then the metal sheet is passed through a pair of hot rollers
which removes excess of Zinc and maintain uniform
thickness of Zinc on metal sheet.
The sheet is subjected to annealing process at 650c and
cooled slowly, in order to remove internal stresses.

Uses of Galvanization: It is used to protect Iron used for

roofing sheets, wires, pipes, nails, bolts, screws, buckets,
and tubes.
Defects :Galvanised utensils are not used for cooking
because of solubility of Zn.
 TINNING
Tinning is the process of coating of tin over the Iron sheet or
steel articles
A cleaned iron sheet is passed through a bath of molten flux,
then passes through a tank of molten tin and finally through a
layer of palm oil which protect hot tin coated surface against
oxidation.
Uses: (1)It is widely used for coating of steel, copper, brass &
bronze etc . It is used to store food stuff, ghee oils, kerosene&
pickels and used for refrigerators equipment.