Mad institute

petroleum department

Corrosion of materials

2023- 2024
 Mad institute
petroleum department

 INTRODUCTION
 Chemical vs. Electrochemical Reactions
 Definition of Corrosion
 CAUSES OF CORROSION
 Effects or disadvantages of corrosion
 Classification of corrosion
 THEORIES OF CORROSION
 Types Of Corrosion
 FACTORS EFFECTING THE CORROSION
 Factors influencing corrosion
 Types of fluid corrosion
 CORROSION CONTROL METHODS
 Prevention and control
 Methods of applications of metal coatings
 Applications of corrosion
 Destruction of a metal by chemical or electrochemical reaction with its
environment.
 Corrosion is defined as destruction of a solid body by chemical or electrochemical
reactions starting from the surface.
 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
 The corrosion problem should be very seriously considered in all those cases
Introduction
• Non-Metals corrode by chemical reactions & metals
mostly by electrochemical reactions.
• Metals are at high energy levels & hence there is natural
tendency to go to the low energy state i.e. they try to form
oxides, hydroxides, carbonates, sulphides etc. depending
on the type of environment to which they are exposed.
Chemical vs. Electrochemical Reactions
• Chemical reactions are those in which
elements are added or removed from a
chemical species
• Electrochemical reactions are chemical
reactions in which not only elements may be
added or removed from a chemical species
but at least one of the species undergoes a
change in the number of valance electron
• Corrosion processes are electrochemical in
nature
 Definition of Corrosion

Corrosion is the degredation 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.
 Corrosion
Corrosion is the primary means by which metals
detreated.
 Most metals corrode on contact with water (and
moisture in the air), acids, bases, salts, oils, and
other solid and liquid chemicals.
Metals will also corrode when exposed to
gaseous materials like acid vapors, formaldehyde
gas, ammonia gas, and sulfur containing gases.
 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.

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

 The process of corrosion is very harmful and is responsible for the

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 billion dollars all over the world.
Classification of corrosion
Dry corrosion
Wet corrosion
 Dry corrosion
Dry corrosion occurs when the metals are exposed to gaseous

environment
 The extent of corrosion & protective values depends on the

following factors:
 1. Chemical affinity between the environment & the metal.

2. Protective value of film.

3. Nature of film formed.

4. Adhesion between the film & the metal surface.

 Formation & Growth Of Film
The formation & growth of films
occur by three successive stages
1. Adsorption
2. Chemisorptions
3. Growth of film
3.1 Growth of non porous film
3.2 Growth of porous film
 Wet corrosion
Wet corrosion occur when a metal or an
alloy comes in contact with an aqueous
solution of salt, acid or alkali by an
electrochemical type of reaction.
When a metal is immersed in an aqueous
electrolyte,it dissolve / dissociate into metal
ion + electron.
• This tendency of metal is called as
electrolytic pressure or solution pressure (p)
 Mechanism Of Wet Corrosion
The reaction at anode is always oxidation reaction
& is associated with the dissolution of metal i.e.
 Metal Metal ions + electron
The reaction at cathode is always a reduction
reaction with no corrosion of cathode & varies
depending on the nature of electrolyte in contact
1. Hydrogen evolution :
2. Oxygen absorption :
Anode & Cathode
Anode
Loss of electron in oxidation
Oxidation always occurs at the anode

Cathode
Gain of electron in reduction
Reduction always occurs at the cathode
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 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.

 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.
 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
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)
 1. Hydrogen gas evolution

 2. Oxygen gas absorption

 1.Hydrogen evolution :
The hydrogen evolution occurs at the
cathode in concentrated acidic environment
(pH < 4) usually iron surface is covered with
oxide at least at few points or it may
difference in hydrogen over potential from
point to point
At the anode :
Fe Fe+2 + 2e ( oxidation)
 At the cathode :
2H+ + 2e H2 (Reduction)
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.
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
 General corrosion

 Water line corrosion

 Pitting corrosion

 Stress corrosion cracking

 Erosion – corrosion

 Galvanic corrosion

 Cavitation corrosion

 Corrosion fatigue )mechanical degradation stress)

 Hydrogen blistering (form of wet H2S damage)

 High temperature corrosion

 General Corrosion

Corrosion proceeds at the same rate throughout the

area exposed to the environment & there is no
clearly defined anode & cathode areas.
The extent of corrosion can be expressed by loss in
weight per unit area or by average penetration depth
 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.
 Pitting Corrosion
Pitting corrosion is a localized accelerated
corrosion resulting in the formation of cavities
around which the metal is relatively unattacked
 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 ( positive).
 The part which has higher oxygen

concentration is cathodic ( negative).

 Stress corrosion cracking
This type of corrosion occurs due to presence of
stresses in the material
 Erosion – corrosion
This type of corrosion can occur in any metal &
alloy.
In many cases, it has been observed that the damage
to the metal is due to the breaking of protective
coating of corrosion product & coating is not get
repaired due to turbulence flow of electrolyte.
This type of corrosion is usually occurs in the regions
where the flow of electrolyte is disturbed e.g. bend in
pipes, condenser tube, valve seat in in water fitting
etc.
 Mechanism
All metals exhibit a tendency to be oxidized, some
more easily than others. A tabulation of the relative
strength of this tendency is called the galvanic series.
 The mechanism involves the formation of a galvanic
cell by diff metals or in diff areas on same piece of
metal.
When galvanic cells are formed on diff metals, the
galvanic corrosion.
 Mechanism
The corrosion process (anodic reaction) of the
metal dissolving as ions generates some electrons
that are consumed by a secondary process (cathodic
reaction).
These two processes have to balance their charges.
The sites hosting these two processes can be located
close to each other on the metal's surface, or far
apart depending on the circumstances.
Corrosion Reaction on Single Metal
Electrochemical reactions are illustrated by
considering the corrosion on a piece of iron in
hydrochloric acid.
Anodic and Cathodic areas are formed on the
surface of iron, owing to surface imperfection
(localized stresses, grain orientation, inclusions
in the metals ) or due to variations in the
environment.
Numerous tiny reactions may occur.
Mechanism
 Corrosion Mechanism
Corrosion is the destructive attack of a metal by
chemical or electrochemical reaction with its
environment.
Corrosive attack of metals is an electrochemical
process.
In a galvanic cell, two dissimilar metals (e.g., iron and
copper) are placed in electrical contact in the presence
of oxygen and moisture.
Separate chemical reactions take place at the surfaces of
the two metals, creating a flow of electrons through the
connecting wire.
 Reaction at anode
Oxidation takes place with the release of electrons.
Positively charged iron atoms get detached from the
solid surface and enter in to solution (electrolyte) as
positive ions.

At Anode: Fe Fe++ + 2 e- (indicating rough

surface)

The released free electrons pass round the external

circuit.
 Reaction at cathode
Reduction of constituents occurs with the
taking up of electrons.
The free electrons reach the cathode and react
with some positively charged species such
hydrogen ions in the electrolyte solution.
In the absence of acid, water itself dissociates to
generate H + ions.
At Cathod : 2 H + + 2e- H2 (indicating
by formation of bubbles at the surface)
 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.
Galvanic Cell
The metal (iron) which is dissolved in the electrolyte is
proportional to the number of electrons flowing, which
in turn is dependent upon the resistance of the metal.

The overall Reaction : Fe + 2H2O Fe(OH)2 +

H2
Red brown rust.
High evolution of H2 accompanies rapid corrosion such
as hydrogen generation.
Depletion of hydrogen also enhance corrosion.
In moderate conc of H2, corrosion slows down.
The actual loss of metal involved in the process takes
place at the anode.
The iron atoms are transformed to ferrous ions (Fe++)
which dissolve in the solution around the anode.
They may diffuse and combine with the hydroxyl ions
(OH-), with the precipitation of ferrous hydroxide
[Fe(OH)2] in accordance with the following net redox
reaction:
2Fe + 2H20  2Fe(OH)2.
The hydrous ferrous oxide formed (FeOH20) is further
oxidized to form hydrous ferric oxide (Fe203 . nH20),
which is rust.
Corrosion Reaction between Metals
Galvanic corrosion result from the flow of current
from a more active metal (anode) to a less active
metal (cathode).
For example, zinc dissolves and forms an anode,
while copper forms the cathode.
These two metals form two electrons electrodes
and their presence in an electrolytic solution froms
galvanic cell.
Spontaneous reaction can occur when two
electrodes are connected through an external wire.
At Anode : Zn Zn++ + 2e- (indicated by rough
surface)
At Cathode : 2H+ + 2e- H2 (indicated by
formation of bubbles at the surface)
The corrosion current flows at the expense of the
anode metal, which gets corroded continuously, where
as the cathode metal is protected.
In some cases, evolution of the hydrogen gas is slow.
The accumulation of hydrogen on the cathode surface
slows down the corrosion.
This is called cathodic polarization.
It forms an insulating layer that slows down or stops
the electrochemical reaction.
 Corrosion Involving Oxygen
The oxygen dissolved in an electrolyte can react with
accumulated hydrogen to form water.
Depletion of hydrogen layer allows corrosion to
proceed.
At cathode: O2 + 2H2 2H2O
Corrosion proceeds due to depletion of Hydrogen.
Above reaction take place in acid media.
When the corrosion media is alkaline or neutral,
oxygen is absorbed. The presence of moisture
promotes corrosion.
The effective conc of oxygen in water adjacent to
cathode depends upon the degree of aeration, temp &
pressure of dissolved salts.
 The factors that effect corrosion are

i) Nature of the metal

ii) Nature of the environment

 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
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).
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 .
Factors influencing corrosion
 Solution pH.

 Oxidizing agent.

 Temperature.

 Velocity.
 Surface Films.

 Other Factors.
 Solution pH
Metals such as iron dissolve rapidly in acidic solution.
In the middle pH range (4 to 10), the conc of H+ ions
is low. Hence, the corrosion rate is controlled by the
rate of transport of oxygen.
Certain amphoteric metals dissolve rapidly in either
acidic or basic solution. E.g. Al and Zn.
Noble metals are not affected by pH. E.g. gold and
platinum.
H+ ions capture electrons and promote anodic
corrosion.
 Oxidizing agents
Oxidizing agents accelerate the corrosion of one class of
materials, whereas retard another class.
Oxidizing agents such as oxygen react with hydrogen to
form water. Once hydrogen is removed, corrosion is
accelerated. E.g. copper in NaCl
Oxidizing agent retard corrosion due to formation of
surface oxide films, which makes the surface more
resistant to chemical attack.
Thus a balance between the power of oxidizing agent to
preserve the protective layer and their tendency to destroy
the protective film determine the corrosion of metal.
 Temperature
Rise in temp increase rate of corrosion.
Increase in temp reduce the solubility of oxygen or
air. The released oxygen enhances the corrosion.
Increase in temp induces phase change, which
enhance the rate of corrosion. At high temp organic
chemicals are saturated with water. as temp
decreases, water gets condensed.
Oxygen is needed for maintaining iron oxide film. In
the absence of O2 corrosion of S.S. increases.
Copper based alloys do not depend on oxide film for
corrosion.
 Velocity
High velocity of corrosive medium increases corrosion.

Corrosion products are formed rapidly, because

chemicals are brought to the surface at a high rate.
The accumulation of insoluble film on the metallic

surface is prevented. So corrosion resistance of these

films decreases.
The corrosion pdts are easily stifled and carried away,

thereby exposing the new surfaces for corrosion.

 Surface Films
The oxide films are formed on the surface of S.S. these films
absorb moisture, which delay time of drying and hence increases
the extent of corrosion.
Insoluble slats such as carbonates and sulphates may be
precipitated from hot solution on the metal surfaces. These
protects the metal surfaces.
If the film is porous (e.g. ZnO) corrosion continues. Nonporous
films (CrO on iron) prevents further corrosion.
Oil and grease films may occur on the surface either
intentionally or naturally. These films protect surface from direct
contact with corrosive substance. E.g. metals submerged in
 Other factor
The conc of corrosive chemicals. In distillation

columns, evaporators, the concentration can change

continuously, so difficult to predict the corrosion rate.
The presence of moisture that collects during cooling

can turn innocuous chemicals into dangerous

corrosives.
Types of fluid corrosion
There are Four Types of fluid
corrosion:
1. Fluid corrosion, General
2. Fluid corrosion, Localized
3. Fluid corrosion, Structural
4. Fluid corrosion, Biological.
 1. Fluid corrosion, General
When corrosion is generally confined to a
metal surface, it is known as general
corrosion.
It occurs in uniform fashion over the
entire exposed surface area.
Two type general corrosion
1. Physicochemical corrosion
2. electrochemical corrosion
 2. Fluid corrosion, Localized
It is most commonly observed on
different locations.
Four types:
A] Specific site corrosion
B] Stress induced corrosion
C] Liquid flow related corrosion
D] Chemical reaction related corrosion
A] Specific site corrosion
Mechanically weak spots or dead spots
in a reaction vessel cause sp site
corrosion.
Three type
1. Inter-granular corrosion
2.Pitting corrosion
3.Crevice corrosion
 a)Inter-granular corrosion
Selective corrosion that occurs in the
grain boundaries in a metal/alloy is
called as inter-granular corrosion.
When it is severe it causes loss of
strength and ductility (flexibility).
E.g. Austenitic S.S + HNO3 grain
boundary ppt.
S.S is stabilized by adding
niobium/titanium (less than 0.03 %).
 b)Pitting corrosion
In this type pits and cavity develops.
They range from deep cavities of small
diameter to shallow depression.
Chloride
E.g. allow of Al/S.S + Aq. Solution
Cavities.
Pitting occur when there is break in
protective oxide layer and
imperfections on the underlying metal.
 c)Crevice corrosion
Here, corrosion take place in crevices bcz
solutions retained at this place and takes longer
time to dry out.
When this occurs, the severity of attack is more
severe at crevices.
Crevices are formed bcz of the metal contact
with another piece of the same or other metal or
with a nonmetallic material.
Corrosion in crevice is due to deficiency of O2,
Acidity changes, Depletion of inhibitor.
Pitting and Crevice Corrosion
 B] Stress induced corrosion
Residual internal stress in metal external applied
stress accelerate the corrosion.
Residual internal force is produced by:
Deformation during fabrication
Unequal rate of cooling from high temp.
Internal stress rearrangement involving volume
changes
Stress induced by rivets, bolts and shrink fits.
Eliminating high stress areas prevent this type of
corrosion.
 a)Stress Corrosion Cracking
At the surface, if the tensile stress is equal to or
more than yield stress, the surface
Develops crack is known as stress
Corrosion cracking.
E.g. cold formed brass develops crack in the
environment of ammonia.
Embrittlement of cracking of steel is observed
in caustic solution.
 b)Corrosion fatigue
Corrosion fatigue is the ability of metal surface to
withstand repeated cycle of corrosion. The metal
surface is stressed and simultaneously attacked by
the corrosive media.
Pits indicating corrosion are formed initially, which
further develops in to cracks.
The protective surface oxide film reduces corrosion.
Under cycling or repeated stress conditions, rupture
of protective oxide films takes place at a higher rate
than at which new protective films can be formed.
So the rate of corrosion is enhanced.
 c)Fretting corrosion
Fretting corrosion occurs when metals slide over
each other and cause mechanical damage to one
or both.
During relative movement of metals, two process
may occur, (i) frictional heat is generated, which
oxidize the metal to form oxide films. (ii) removal
of the protective films resulting in exposure of
fresh surface to corrosion attack.
This can be avoided by using harder materials,
minimizing friction by lubrication or by proper
designing of the equipment.
 C] Liquid Flow related corrosion
Liq. Metals can cause corrosion.
The driving force is the tendency of the
liq. To dissolve solids or penetrating the
metal along the grain boundaries at place
of wetting.
E.g. mercury attack on Al alloy
Molten Zinc on S.S.
 a)Impingement corrosion
Also referred as erosion corrosion or
velocity accelerated corrosion.
It is accelerated by removal of
corrosive products, which would
otherwise tend to stifle the corrosion
reaction.
 b)Erosion corrosion
Erosion is the destruction of metal by abrasion
and attrition caused by the flow of liq./gas.
Factors that influence erosion
1. Alloy content of the steel (e.g. Cr, Cu, Mn)
2.Pipe system design and component geometry.
3.Water and steam composition (especially pH
and oxygen content).
The use of harder metals and changes in velocity
or environment are used to prevent erosion.
 c)Cavitation corrosion
Formation of transient voids or vacuum bubbles
in a liquid stream passing over a surface is known
as cavitation.
The bubble may collapse on the metal surface
thereby causing severe impact or explosive
effect.
So considerable damage and corrosion is
observed.
Cavitation corrosion is also observed around
propellers, rudder in pumps etc.
D] Chemical Reaction related corrosion
Corrosion involves chemical reactions
such as oxidation and reduction.
Galvanic corrosion
Oxygen conc cell
Hydrogen embrittlement
 a)Galvanic corrosion
It is associated with the flow of current to
a less active metal from a more active metal
in the same environment.
Coupling of two metals, which are widely
separated in the electrochemical series,
generally produces an accelerated attack on
the more active metal, zinc.
 b) Oxygen conc cell
It is due to the presence of oxygen
electrolytic cell.
i.e. diff in the amt of oxygen in solution at
one point exists when compared to
another.
Corrosion is accelerated when the O2 is
least, for example, under gasket, stuffing
boxes etc.
 c)Hydrogen embrittlement
hydrogen can penetrate carbon steel and react
with carbon to form methane.
The removal of carbon result in decreased
strength.
Corrosion is possible at high temp as significant
hydrogen partial pressure is generated.
This cause a loss of ductility, and failure by
cracking of the steel.
Resistance to this type of attack is improved by
allowing with chromium / molybdenum.
 c)Hydrogen embrittlement
Hydrogen damage can also result from H2
generated by electrochemical corrosion
reaction.
The result is failure by embrittlement,
cracking, and blistering.
This is observed in solution of sp weak
acids such as hydrogen sulphide and HCN.
 3.Fluid corrosion: Structural
Here, the strength is reduced on account
of corrosion.
This may occur when one component of
the alloy is removed or released into
solution.
The corrosion pdt may retain in the plant.
E.g. Graphite corrosion
Dezincification
 a)Graphite corrosion
Graphite is allotropy of carbon.
Graphite corrosion may occur in gray cast iron.
Metallic iron is converted in to corrosive pdts
leaving a residue of intact graphite mixed with
iron corrosive pdts and other insoluble
constituent of cast iron.
When the layer of corrosion is impervious
corrosion will cease.
If layer is porous corrosion will be greater.
 a)Graphite corrosion
When carbon steel is heated for prolonged
periods at temp greater than 455 C, carbon
may segregated, which is then transformed
in to graphite. So the structural strength of
the steel is affected.
Employing killed steels of Cr and
Molybdenum or Cr and Ni can prevent this
type of corrosion.
 b)Dezincification :
It is seen in brass containing more than 15 %
zinc.
In brass the principle pdt of corrosion is
metallic copper, which may redeposit on the
plant.
Another mechanism involves the formation of
zinc corrosion pdts.
Corrosion may occur as a plug filling pits or as
a continuous layer surrounding the unaffected
core of brass.
It can be reduced by addition of small amt of
arsenic, antimony or phosphorus to the alloy.
 4. Fluid corrosion : Biological
The metabolic action of M.O. can either directly
or indirectly cause deterioration of a metal. Such a
process is called as a biological corrosion.
The cause of biological corrosion are:
1. Producing corrosive environment or altering
environment composition.
2.Creating electrolyte conc cells on the metal
surface.
3.Altering resistance to surface films.
4.Influencing the rate of cathodic/ anodic reaction.
The role of biological corrosion may be explained
by sulphate reducing bacteria in slightly acidic or
alkaline soils.
Reducing
bacteria Calcium
Hydrogen
Sulphate Sulphite
Sulphite
Anaerobic

On Iron
in Soil

Iron Sulphide
Corrosion pdt
 Corrosion control methods
The various measures taken for corrosion protection are

I) CATHODIC PROTECTION

II) SURFACE COATINGS

Prevention and control
The corrosion may be prevented or controlled by
following ways:
1. Selection of proper material
2. Proper design of equipment
3. Altering environment
4. Inhibitors
5. Cathodic protection
6. Anodic protection
7. Coating and lining
 1. Selection of proper material
Corrosion should not be permitted in fine wire screen,
orifice and other items in which the dimensions are
critical and change is not permitted.
In some cases, non metallic materials will be more
economic and have good performance. It should be
considered if their strength, temp and design is
satisfactory.
The corrosion characteristics of chemicals and
limitation of construction material can be considered.
The processing conditions should also be considered.
 2. Proper design of equipment
In the design of equipment, the number of fittings
like, baffles, valves and pumps should be considered.
Corrosion can be minimized if the equipment design
facilitates
Elimination of crevices
Complete drainage of liquids
Ease of cleaning
Ease of inspection and maintenance
A direct contact between two metal is avoided, if
they are seperated widely in elecrochemical series. Or
they should be insulated.
 3. Altering Environment
Corrosion can be reduced by employing following
conditions:
1. Removing air from boiler feed water prevents
the influence of water on steel
2. Reducing the temp
3. Eliminating moisture
4. Reducing the velocity of turbulence
5. Shortening the time of exposure
6. Pumping the inert gas into solutions
7. Reducing aeration.
 4. Inhibitors
The corrosion inhibitors are added to the
environment to decrease corrosion of metals.
This form protective films.
1. Adsorption type, e.g. adsorbed on metal
2.Scavenger phase type, e.g. remove corrosion
agent
3.Vapor phase type, e.g. sublime and condense on
metal surface.
Inhibitors are generally used in quantities less
than 0.1 % by weight.
e.g. of inhibitors
1. Chromate, Phosphates & Silicates protect iron
and Steel in aq solution.
2.Organic sulphide and Amines protect iron and
Steel in acidic solution.
3.Copper sulphate protects S.S in hot diluted
solution of H2SO4.
 5. Cathodic protection
It is based on the galvanic action between the
metals of the anode and cathode suspended in
the solution.
The metals to be protected is made a cathode.
Electrons are supplied , there by dissolution of
metal is suppressed.
The method of protecting metals and alloys from
corrosion making them completely cathode.
To achieve this auxiliary anode is provided in the
corroding medium which is connected to the
structure.
 It can be achieved by (Cathodic protection is of two types):

1. Sacrificial anode method (Approximate anodic method )

2. Impressed emf method (Impressed current cathodic method )

1. Sacrificial anode method
(Approximate anodic method )
In this method, anodes are kept in electrical contact
with the metal to be protected.
The anodes are sacrificed, since it goes into solution.
E.g. for the protection of iron and steel tanks, the
metals such as Zinc, Al, Mg and their alloy are used as
sacrificial anodes.
This are used in limited pH range.
Anode metal is selected from electrochemical series.
The anodes should not be poisonous and not
detrimental to the pdts.
 *** Force the metal to be protected to behave like cathode.
-Approximate 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 an

anode (Zn-blocks) which undergoes corrosion leaving the base
metal protected.

Eg. The underground water pipelines and water tanks are also
protected by this method. By referring to the electrochemical
series, the metal with low reduction potential is connected to the
base metal which acts as anode.
2. Impressed emf method (Impressed
current cathodic method )
It is also known as applied current system, i.e.,
external voltage is impressed between tank and
electrodes.
The negative terminal of power is connected to the
material to be protected.
So the natural galvanic effect is avoided and the
anode is maintained positive.
Since anode is not consumed, metal or non
corrodable material can be used.
 Direct current is applied in opposite direction to cancel the
corrosion current
 Converts the corroding metal from anode to cathode.
 Advantages
This method is used for large tanks to
store mild corrosive liquors. In these cases,
mild steel is used with negligible corrosion.
Cathodic protection method is simple and
the most effective.
It is inexpensive. It enables the use of
cheaper material for plant construction.
Disadvantage: Corrosion can not be
reduced to zero.
 6. Anodic Protection
In this method, a predetermined potential is applied
to the metal specimen and the corresponding current
changes are observed.
During the initial stage, the current increases
indicating the dissolution of the metal.
When the current reaches a critical point,
passivisation occur, i.e., the oxide layers set in
suitable oxidizing environment. The potential at the
critical point is called passivating potential.
Above this passivating potential, the current flows
decreases to a very small value called passivating
current.
The passivating current is defined as the
minimum protective current density
required to maintain passivisation.
At this stage, an increase in potential will
not be corrode the metal since the later is
in highly passive state.
E.g. in case of S.S. titanium becomes easily
passive and can not offer cathodic
protection.
Advantages :
The anodic protection method is
utilized in the transportation of conc
H2SO4.
Disadvantages:
Corrosion can not be reduced to zero.
This method cannot be applied for
metals, which do not passivate.
 7. Coatings and Linings
Nonmetallic coatings and linings can be applied on
steel and other materials of construction in order to
combat corrosion.
Coating methods: electroplating, cladding, organic
coating.
The thickness of lining is important.
Effective linings can be obtained by bonding
directly to substrate metal or building multiple
layers.
Organic coatings can be used in tanks, piping and
pumping lines.
A thin non-reinforced paint like coating of less
than 0.75 mm thickness should not be used in
services for which full protection is required.
The cladding of steel with an alloy is another
approach to this problem.
Sp glass can be bonded to steel so that the liner
is 1.5 mm thick which is impervious.
Piping and equipment lined in this manner are
used in severely corrosive acid services.
 The metal surface is covered with a coating to protect it from
corrosion.
 These may be
i) Metallic
ii) Organic
 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 flow cleans the base metal& prevent oxidation of metal
coating with molten solution.
 Hot dipping is widely applied either by
(1) Galvanizing (2) Tining
 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 minutes at (60-90)0c. The steel is then washed well and

dried .
 Then the metal sheet is dipped in bath of molten Zinc maintained

at (425 – 430)0c.
The surface of bath is kept covered with a Zncl 2
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.
Tinning is the process of thinly
coating sheets of iron or steel
with tin, and the resulting product
is known as tinplate. The term is
also widely used for the different
process of coating a metal with
solder before soldering.
Electroplating:
Deposition of coating metal on the base metal by passing
direct current through an electrolytic solution which contain
the soluble salts of the coating material.
Pure metal is made as cathode and base metal as anode.
Electrochemically coat metal is deposited on base metal.
This metal gives smooth, fine and uniform coating
It depends on
(i) Temperature

(ii) Current density

(iii) Electrolyte Concentration

(iv)Nature of base metal (v) Time

 It is most important & frequently used technique in industries to
produce metallic coating

 Both metals & non metals can be electroplated.

 In metals the electroplating increases resistance to corrosion,

chemical attack, hardness, wear resistance and surface properties.

 In non metals electroplating increases strength and decorates the

surface of non metal like plastics, wood, glass.
 Paints form a protective layer over the surface of the metal to
prevent corrosion.
The main constituents of the paints are
 Pigment
 Vehicle
 Thinner
 Driers
 Fillers
 Plasticizers
 Anti skinning agents
 It is a solid constituent that obscures the surface and provides a
decorative color.

 A liquid binds the pigment to the surface and protects it from

decay.

 It usually comprises of 60 to 80% of the weight of the paint film.

 Increases the life of paint film since it prevents the entry of ultra
violet rays.

 E.g.; lead oxide, red lead, lead chromate etc.,

 Film forming constituent of the paint.

 They hold the pigment on the metal surface.

 They give metal adhesion to the metal surface.

 They impart durability and toughness to the film.

 They isomerize , polymerize and condense to form characteristic

tough, elastic ,coherent, highly cross linked structured
macromolecular film.

 E.g.: mustard and sunflower oil etc.,

 Viscosity is reduced by the addition of thinners.

 It is a volatile solvent helps to adjust the consistency of the paint.

 Thinner being volatile evaporates.

 They remain permanently in paints and varnishes.

 They improve elasticity of the film.

 They suspend the pigments in the paints.

E.g. Turpentine, mineral spirits, xylol, kerosene.
 They are inert materials.

 They are used to improve the properties of the paints.

 They reduce the cost of paints.

 They serve to fill the voids in the film.

 Increases the random arrangement of pigment particles.

 Improves the durability of the film.

 E.g.: talc, chalk, silica etc.,

 Drying of the oil film is accelerated or catalyzed by driers.

 To reduce the drying time a drier is added.

 They are oxygen carrier catalyst.

 To improve the drying quality of oil film.

 This is done by condensation , oxidation and polymerization.

E.g. linoleates , borates, resinates etc.,
 They remain permanently in paints and varnishes.

 They improve elasticity of the film.

 To prevent cracking of the film.

 Anti skinning agents prevent the gelling and skinning of

the paint film.

E.g.: tricresyl phosphate, tri phenyl phosphate,

di butyl tartarate etc.,
Applications of corrosion