Unit - Ii Corrosion and Corrosion Control

Corrosion and Corrosion control 3.
UNIT – II
CORROSION AND
CORROSION CONTROL
3.1 INTRODUCTION
Corrosion can be defined as the loss of materials as a
result of chemical or electrochemical reaction with the
environment. The annual cost of corrosion in India is around
Rs. 600 crores. The loss due to corrosion include the cost of
repair or replacement of the corroded component or equipments.
By making proper use of existing corroded materials and
techniques for corrosion prevention, about 25% of the estimated
amount (Rs. 150 crores in India) can be saved.
Now a days it is necessary to pay more attention to

corrosion because of increasing use of metals in all fields of
technology and increase in air and water pollution there by
resulting in a more corrosive environment.
Definition :
Metals combines with oxygen gives metal oxide is called
corrosion.
Destruction of metals (or) deterioration of metals by the
attack of environment is called corrosion.
Causes of corrosion
Metals occur in nature are in the following two forms :
1. Native state
The metals occur in native (or) free (or) uncombined state
are non-reactive with the environment. They are noble metals
3.2 Applied Chemistry
exist as such in the earth crust they have very good corrosion
resistance.
Example : Au, Pt, Ag, etc.,
2. Combined State
Except noble metals, all other metals are reactive and
react with environment and form stable compounds, as their
oxides, sulphides, chlorides, and carbonates. They exist in their
form of stable compounds called ores and minerals.
Example : Fe2O3, ZnO, PbS, CaCO3, etc.,
The metal ores are converted into pure metal by the use of
metallurgical process. The pure metal at higher energy will
always have a tendency to go into the lower energy state by the
attack of environment is called corrosion.
Metallurgical Process
Metal ore (Reduction) Pure metal
(Impure form) (Higher energy state)
Corrosion
(Less Stable) (Oxidation) (More Stable)
3.2 CLASSIFICATION OF CORROSION
The corrosion process is classified on the basis of

mechanisms.
(i) Dry corrosion (or) Chemical corrosion
(ii) Wet corrosion (or) Electro chemical corrosion
3.2.1 Dry Corrosion (or) Chemical Corrosion

This type of corrosion occurs through direct chemical
action of dry gases (or) corrodents such as oxygen, halogen, H2S,
SO2, etc.,
Corrosion and Corrosion control 3.3
This can be classified as follows,
(1) Corrosion by oxygen (Oxidation corrosion)

Oxygen present in the atmosphere attacks metal
surface resulting in the formation of metal oxide which is known
as corrosion product and this process is known as oxidation
corrosion.
Mechanism
2-
O
inward diffusion of
oxygen through scale
Outward diffusion of
metal ions through 2+
scale M
(Metal)
Fig : 3.1 Oxidation corrosion
Oxidation first occurs at the surface of the metal resulting

in the formation of metal ions (M2+)
M M2+ + 2e (Oxidation)
Oxygen is converted to oxygen ion (O2-)

- 2-
½O2 + 2e O (Reduction)
Metal ions combines with oxygen ions forms the metal oxide film
M + ½O2 M2+ + O2- MO (Metal Oxide)

Nature of the metal oxide films formed
There are generally four types of metal oxide films are

formed.
(i) Stable film

If the oxide film is stable, there is no further penetration
of oxygen ions to the metal part. There is no further corrosion
takes place. Thus the stable film act as protective coating.
Examples : Al, Sn, Pb, Cu, etc.,
(ii) Unstable film

In the case of noble metals the metal oxides formed
decomposes reversibly to the metal and oxygen.
Metal oxide Metal + Oxygen
In this case, the corrosion is a continuous process.
Examples :
Pt, Ag, Au, etc.,
(iii) Porous film

The oxide layer formed in some cases are porous. In this
case atmospheric oxygen can easily move to the metal surface.
So corrosion is a continuous process.
Examples :
Li, Na, K, etc.,
(iv) Volatile film

The oxide layer formed in some cases are volatile. So the
oxide film volatises as soon as they are formed. The fresh metal
surface is kept exposed all the time for further attack. Thus it act
as a non-protective coating.
Example :
Molybdenum oxide film.
Pilling - Bed Worth rule

An oxide layer is protective (or) non-porous, the volume
of the metal oxide formed is greater than the volume of the metal.
An oxide layer is non-protective (or) porous, the volume
of the metal oxide formed is less than the volume of the metal.
(i) Stable film

If the oxide film is stable, there is no further penetration
of oxygen ions to the metal part. There is no further corrosion
takes place. Thus the stable film act as protective coating.
Examples :
Al, Sn, Pb, Cu, etc.,
(ii) Unstable film

In the case of noble metals the metal oxides formed
decomposes reversibly to the metal and oxygen.
Metal oxide Metal + Oxygen
In this case, the corrosion is a continuous process.
Examples :
Pt, Ag, Au, etc.,
(iii) Porous film

The oxide layer formed in some cases are porous. In this
case atmospheric oxygen can easily move to the metal surface.
So corrosion is a continuous process.
Examples :
Li, Na, K, etc.,
(iv) Volatile film

The oxide layer formed in some cases are volatile. So the
oxide film volatises as soon as they are formed. The fresh metal
surface is kept exposed all the time for further attack. Thus it act
as a non-protective coating.
Example :
Molybdenum oxide film.
Pilling - Bed Worth rule

An oxide layer is protective (or) non-porous, the volume
of the metal oxide formed is greater than the volume of the metal.
An oxide layer is non-protective (or) porous, the volume
of the metal oxide formed is less than the volume of the metal.
Protective layer metals e.g., Al, Sn, Pb, Cu, etc,.

Non protective metals e.g., Li, Na, K, Mg, Ca, Sr, etc,.
b) Corrosion by other gases

Other gases present in the atmosphere like SO2, CO2, Cl2,
H2S etc,. can also attack the metals.
For example,
1. Chlorine attacks on silver forms protective layer of silver
chloride, it prevents further corrosion.
Cl2 + 2Ag 2AgCl

2.But Sn reacts with chlorine present in the atmosphere forms
SnCl2.It is volatile. So the corrosion is a continuous process.
Cl2 + Sn SnCl2
3.Metals combines with H2S gas to liberate atomic hydrogen.

H2S + Fe FeS + 2H (atomic hydrogen)
The atomic hydrogen is very reactive and penetrate the

metal and occupies the voids of the metal.
The atomic hydrogen recombines inside the metal and

develop pressure which leads to cracking of the metal. This is
known as “Hydrogen Embrittlement”.
4.Atomic hydrogen are formed by dissociation of H 2 gas at high

temperature.
H2 H+H
5. The atomic hydrogen is highly reactive and combine with

carbon present in the metal forms CH4 gas which leads to
cracking of the metal surface. This is known as
“Decarburisation”.
c) Liquid metal corrosion

This type of corrosion is due to the chemical action of
flowing liquid metals at high temperature on solid metal.
Such type of corrosion are found in nuclear power plants.
3.2.2 Wet Corrosion (or)

Electrochemical Corrosion
This type of corrosion occurs when,
(i) The conducting electrolytic liquid is in contact with metal.
(ii) Two dissimilar metals are partially dipped in the electrolyte.
In the above condition one part of the metal becomes

anode and the remaining part becomes cathode.
In anodic area
Oxidation takes place with the liberation of electrons.
M M2+ + 2e-
In cathodic area
Depending upon the nature of electrolytic solution, two
types of reaction takes place at cathode.
(i) Hydrogen evolution mechanism

(ii) Oxygen Absorption mechanism
This can be explained as follows,

(i) Hydrogen evolution mechanism

When the conduction medium is highly acidic or
completely free from dissolved oxygen, hydrogen evolution takes
place. For example, corrosion of iron metal by industrial waste
containing H+ ion undergoes this type of corrosion.
In this type of corrosion, anodes possess large surface

area and less cathode area.
Anodic solution (electrolyte)

Small cathodic area
Anode
Fig : 3.2 Hydrogen Evolution
2+ -
At anode : Fe Fe + 2e (Oxidation)
+ -
At cathode : 2H + 2e H (Reduction)
2
+ 2+
Overall : Fe + 2H Fe +H2
(ii) Oxygen Absorption mechanism

This type of mechanism takes place when base metals are
in contact with neutral solution like H2O with dissolved oxygen.
An example of this kind of corrosion is the rusting of paint coated
iron. If there is any crack in the paint coated iron, that area acts as
anode.
Cathode
Corrosion
product (rust)
Small anodic area
Cathode
Fig : 3.3 Oxygen Absorption

The liberated electrons flows from the anode to the

cathode through the metal and accepted along the electrolyte and
oxygen at cathode.
2+ -
At cathode : ½O2 + H2O + 2e 2OH (Reduction)
Overall :
-
Fe + ½O2 + H2O Fe2+ + 2OH Fe(OH)2 (corrosion product)
If enough oxygen is present, ferrous hydroxide is

converted into ferric hydroxide.
4Fe(OH)2 + O2 + H2O 4Fe(OH)3 (Rust)
Table 3.1 Differences Between Chemical and Electro

Chemical Corrosion
Sl. Dry (or) Wet(or)Electro Chemical
No Chemical Corrosion Corrosion
1. It occurs in dry state It occurs in presence of
moisture (or) electrolyte
2. It follows adsorption It follows the mechanism of
mechanism electro chemical reaction.
3. Corrosion product Corrosion occurs at anode
accumulate on the same while products gather at
spot, where corrosion cathode
occurs.
4. Uniform corrosion Localised corrosion occurs.
behaviour is seen, i.e., i.e., one metal surface alone
either the whole surface of is corroding even though
the metal in contact with both metal surfaces are in
the medium corrodes, or it contact with the medium.
does not.
5. Only heat evolution can be Due to electron flow from the
observed. site of oxidation to site of
reduction, current flow can
be observed.
3.2.3 Galvanic Corrosion

This type of electrochemical corrosion takes place when two
dissimilar metals are joined in the presence of electrolyte. The
metal with higher negative electrode potential acts as anode and
the remaining parts acts as cathode.
Electrolyte (Cathode)
Zn Fe
Anode Cathode
Fig : 3.4 Galvanic corrosion (Zn / Fe)

2+
At anode : Zn Zn + 2e (Oxidation)
At cathode : ½O2 + H2O + 2e 2OH (Reduction)
Overall : Zn + ½O2 + H2O Zn2+ + 2OH Zn(OH)2
Electrolyte (Cathode)
Fe Cu
Anode Cathode
Fig : 3.5 Galvanic corrosion (Fe / Cu)

2+
At cathode : ½O2 + H2O + 2e 2OH
Overall : Fe + ½O2 + H2O Fe2+ + 2OH Fe(OH)2

The galvanic corrosion can be avoided by
1. Coupling of metals very close in the emf series.

2. Providing an insulating material between the two metals.
3.The area of the cathode is always smaller than anodic area.
3.2.4 Concentration Cell Corrosion (or)

Differential Aeration Corrosion
This is the most common type of electrochemical
corrosion that takes place when the metal is partially dipped in
solutions, metals partially covered with dust, sand, water drops
etc. The less aerated part act as anode and the more aerated part
act as cathode. The anodic part undergo corrosion and the
cathodic part is prevented. This type of corrosion called as
Concentration Cell Corrosion.
Example : 1
When a metal is partially immersed in a solution it has
very poor aeration when compared with the metal that is outside
the solution.
More oxygenated
part (cathode)
Electrolyte Less oxygenated

part (anode)
Fig. : 3.6 Concentration cell corrosion (Metal / Electrolyte)
The less aerated part act as anode and the more aerated
part act as cathode.
Example: 2
The another example of this type of corrosion is the
metal parts partially covered with dust, sand, water drops etc.
This type of corrosion is called as pitting corrosion.
Pitting Corrosion
Pitting is a localized attack, resulting in the formation of a
hole around which the metal is relatively unattached.
Cathode
Fig Pitting Corrosion
The area covered by the drop of water act as an anode due

to less oxygen concentration and suffers corrosion. The
uncovered area (freely exposed to air) act 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.
2+
At cathode : ½O2 + H2O + 2e 2OH
Overall
[O]
Fe + ½ O2 + H2O Fe2+ + 2OH- Fe(OH)2 Fe(OH)3
This type of intense corrosion is called pitting.
Example: 3
Differential aeration corrosion may also occur in different
parts of pipeline. The buried pipelines (or) cables passing from
one type of soil to another, say, from clay (less aerated) to sand
(more aerated) may get corroded due to differential aeration.
Example: 4
This type of corrosion is also takes place in wire fence. In
this case the areas where the wires cross are less aerated
than the other parts of the fence. The corrosion takes place at the
wire crossings because less aerated part act as anode.
Cathode
Cathode Anode Cathode
Cathode
Fig. 3.8 : Corrosion on wire fence
3.3 STRESS CORROSION
Stress corrosion is the combined action of a tensile stress and the

corrosive environment on a metal. This type of corrosion is seen
in fabricated articles of certain alloys due to stress, but pure
metals are immune to stress corrosion.
Conditions for stress corrosion to occur:

i) due to the presence of tensile stress
ii) A specific corrosive environment such as

a) For mild steel- caustic alkali & strong nitrate solution.
b) For brass –traces of ammonia solution.
c) For stainless steel-acid chloride solution.
Stress corrosion is an electrochemical corrosion.

Presence of stress in a metal ( due to bending ) produces
strains, which forms anodic part, while the remaining part
acts as cathodic part.
Corrosion reactions
At Anode : Fe  Fe2+ + 2e-
1
At Cathode : O2  H 2 O  2e   2OH 
2
(O)
Net reaction : Fe 2  2OH   Fe(OH ) 2 Fe(OH ) 3
Thus the stressed part is easily attacked, even by a mild

corrosive environment, resulting in the formation of crack.
Stress corrosion
Fig
Prevention
i) Giving suitable treatment to relieve internal stresses.
ii) Adjusting the composition and eliminating impurities.
iii) Selecting more resistant material
iv) Removing corrosive environment.
Examples of Stress Corrosion
1. Season Cracking
Seasonal cracking is a term applied to stress corrosion of copper

alloys (brass).
This corrosion is due to the high residual stresses present
in the brass as a result of cold working. These stresses make the
bras more susceptible to intergranular corrosion in presence of
ammonia or amines.
i.e., Cu + 4 NH3 [ Cu(NH3)4]2 + (soluble)
This is the real cause of dissolution of brass, which is the

reason for cracks.
2. Caustic embrittlement
It occurs in mild steel, when it is exposed to alkaline
solutions at high temperatures and stresses.
Boiler water usually contains a certain proportion of
sodium carbonate, added for water softening purposes. In high
pressure boilers this breaks up to give sodium hydroxide and

carbon dioxide.
Na2CO3 + H2O 2NaOH + CO2 
The NaOH flows into the minute hair cracks and crevices
usually present on the boiler material by capillary action and
dissolves the surrounding area of iron as sodium ferroate.
Fe + 2NaOH Na2FeO2 + H2 
This causes brittlement of boiler parts, particularly stressed parts

like bends, joints, rivets, etc., causing failure of the boiler.
Prevention
1. by adding sodium sulphate to the boiler water instead of
sodium carbonate.
2. By adding tannin, lignin to the boiler water which blocks
the hair cracks.
Soil or underground corrosion

Factors influencing soil corrosion
The various factors that influences soil corrosion are
i) Acidity of the soil
ii) Moisture and electrolyte contents.
iii) Presence of micro-organisms and bacterias.
iv) Content of organic matter
v) Texture ( physical properties) of the soil
Classification of soil corrosion

Based on the particle size, soils are classified into the
following six types.
1. Gravel or Sandy soils

Soils rich in gravel and sand are more porous and hence are
generally more aerated. If a metal pipe is buried in such a soil,
the corrosive conditions are similar to those of oxygen
concentration cell corrosion, the rate of corrosion is governed by
the amount of moisture content in the soil.
2. Water- logged soils

Water-logged soils contain very small amount of free oxygen, but
various bacterias and micro-organisms can grow. This leads to
micro-biological corrosion.
3. Intermediate character soils

This type of soil may produce a localized corrosion. If air
pockets are present, differential aeration corrosion may occur in
different parts.
4.Soil with large amount of organic matter
If the soil contains large amount of organic matter, the
formation of soluble metal complexes and peptization of
corrosion product may accelerate the corrosion process as
compared to the soils, which are relatively free from organic
matter.
5.Non-acids soils
In non-acid soils, the conductivity ( which depends on moisture
and electrolyte content) is the major factor governing the
corrosive character. In such soils, corrosion follows differential
aeration type corrosion. The rate of corrosion mainly depends on
i) the resistance between the anodic and cathodic areas.
ii) the rate of arrival of the oxygen to the cathodic areas.
Thus, when a pipe passes under a paving, the portion under the
paving has less access to oxygen than the one lying under
unpaved soil. Hence, the portion under the paving becomes
anodic and suffers corrosion.
6. Highly acidic soils
In highly acidic soils, the conductivity is not of much importance.

In such soils, corrosion follows hydrogen evolution type
corrosion. The rate of corrosion mainly depends on
i) the pH of the soils
ii) the presence of salt and oxygen etc.,
Water line corrosion

Water line corrosion is also called as differential aeration
corrosion leading to the formation of oxygen concentration cell.
It occurs due to the storage of water in a metal container.
Example:
Water stored in a steel tank (Fig )
Fig water line corrosion
When water is stored in a steel tank, corrosion occurs along the

line just beneath the water meniscus. The highly oxygenated area
( above the water line) acts as the cathode and is unaffected by
corrosion, while the poorly oxygenated area ( beneath the water
line) acts as anode and highly affected by corrosion.
Corrosion reactions
At Anode : Fe  Fe2+ + 2e-
1
At Cathode : O2  H 2 O  2e   2OH 
2
(O)
Net reaction : Fe2+ + 2OH  Fe(OH)2 Fe(OH)3
Draw back: Water line corrosion is a serious problem for ocean

going ships.
Prevention: using special “ antifouling paints”.
Microbiological corrosion
Corrosion caused by the metabolic activity of various
micro-organisms is called microbiological corrosion. The
micro-organisms can develop and propagate in an environment in
the presence (or) absence of oxygen. Therefore they are termed
as aerobic corrosion and anaerobic corrosion.
Types of micro-organism ( microbiological corrosion)

Following three types of micro-organisms are responsible for
microbiological corrosion.
1. Aerobic micro-organism ( aerobic corrosion)
a) Sulphur bacteria ( e.g., thiobacillus)
It oxidizes sulphur present in their cells to give sulphuric acid,
which attack the metals like iron. This type of bacterias grow in
acidic conditions of pH from 0 to 1.
b) Iron and manganese micro-organisms

These bacterias live by taking into their cells iron and
manganese ions. The bacteria digest them in the presence of
oxygen, forming insoluble hydrates of iron and manganese
dioxide, which are then thrown out their bodies. Iron bacterias
grow in stagnant or running water at 5 to 40 oC and pH from 4 to
10.
II) Anaerobic micro-organisms (Anaerobic corrosion)
a) Sulphate reducing bacterias ( e.g., sporovobrio
desulphuricous)
They are responsible for anaerobic corrosion of iron and steel.

They require sulphate and oxygen for their nourishment. The
optimum conditions for their growth are 25-30oC and pH from 5
to 9.
Mechanism
Anodic solution of iron
8H2O  8H+ + 8OH-
4Fe + 8H+  4Fe2+ + 8H
Depolarization due to activity of bacterias

H2SO4 + 8H+  H2S + 4H2O
Corrosion product
Fe2+ + H2S  FeS + 2H+
3Fe2+ + 6OH-  3Fe(OH)2
III) Film forming micro-organisms

Example : Bacterias, fungi, algae & diatoms
This type of micro-organisms form microbiological film on an

iron surface, which can take acids, salts and gases from the
surface of iron, leading to the formation of local biological
concentration cells and consequent corrosion.
3.3 INTERGRANULAR CORROSION
Introduction
This type of corrosion is due to the fact that the grain
boundaries contain material which shows electrode potential
more anodic than that of the grain centre in the particular
corroding medium.
This may be due to precipitation of certain compounds at

the grain boundaries, thereby leaving the solid metal solution
impoverished (or) depleted in one constituent.
The impoverished solid solution is anodic with respect to
the grain centres as well as to the precipitated compound, so that
it will be attacked preferentially by the corrosive environment.
Fig. 3.9 General intergranular attack
This type of corrosion is generally encountered in alloys.
For example,
During the welding of stainless steel (an alloy of Fe, C
and Cr), chromium carbide is precipitated at the grain boundaries,
thereby, region just adjacent to grain boundaries becomes
depleted in chromium composition and is more anodic with
respect to the solid solution within the grain.(which is richer in
chromium).
Intergranular corrosion follows the path of grain boundaries and

occurs on microscopic scale, without any apparent external signs
of any intensive attack. On account of this, sudden failure of
material occurs (without any pre-washing) due to loss of
cohesion between grains.
Remedy
The remedy is proper heat-treatment, followed by rapid
quenching to avoid the heterogeneous precipitation that, usually,
occurs due to slow-cooling.
3.4 FACTORS INFLUENCING RATE OF
CORROSION
Corrosion is a kind of reaction that takes place in the
metal by the influence of its environment. Hence both (i) the
nature of the metal & (ii) the nature of environment play equal
part in the corrosion of the metal. The following are the factors
responsible for the corrosion.
I. Nature of the Metal

(a) Position of metal in the EMF series
Metals higher (-) in the galvanic series undergo strong
corrosion and lower (+) in the EMF series undergo less corrosion.
(b) Relative areas of anode and cathode

Corrosion will be severe if the anodic area is small and
the cathodic area is large. Larger cathodic area of the cathode will
create demand of more electrons, which can be met by the
smaller area of the anode only by undergoing more corrosion.
(c) Over potential

Corrosion is very slow if hydrogen over voltage of the
cathodic metal is high. The over potential of a metal in a
corrosive environment is inversely proportional to corrosion rate.
(d) Nature of the surface film

Stable oxide film restricts further corrosion. Unstable,
volatile and porous oxide films enhances further corrosion.
(e) Purity of the metal

Impurity present in pure metal creates heterogenity and

leads to galvanic corrosion. If the percentage of purity increases
the corrosion rate decreases.
(f) Stress
Metals part under stress can become anode and undergo
corrosion. This type of corrosion is called stress corrosion.
II. Nature of the Environment
(a) Temperature
Increase of temperature increases diffusion of ions in the
corrosive medium and thus rises the corrosion rate.
(b) Humidity
Concentration of water vapour present in the atmosphere
is known as humidity. If the humidity increases the corrosion
rate increases, at a particular point a sudden increase in the
corrosion rate is observed, that is called critical humidity.
Corrosion Rate
Critical Humidity
Humidity
Fig. : 3.10 Critical Humidity
(c) Presence of Corrosive gases

Corrosive gases like SO2, H2S, fumes of HNO3, H2SO4,
acetic acid etc, enhances the corrosion rate.
(d) Presence of suspended solids
Suspended particles like chemically active, chemically

inactive
and chemically neutral dust particles enhances the corrosion rate.
(e) pH
The corrosion rate is maximum when the environment is
more acidic (pH=5) and minimum when the environment is more
alkaline (pH=11). In general, acidic medium is more corrosive
than alkaline or neutral medium.
3.5 CORROSION CONTROL METHODS
The corrosion is controlled by the following methods.

(i) Sacrificial anodic protection
(ii) Impressed current cathodic protection
iii) Control of corrosion by modifying the metal
(iv) Corrosion Inhibitors.
3.5.1 Sacrificial Anodic Protection Method

In this method, the metallic structure to be protected is
made cathode by connecting it with more active metal (anode
metal). So that all the corrosion will concentrate only on the
active metal. The artificially made anode thus gradually corroded
protecting the original metallic structure. Hence, this process is
otherwise known as sacrifical anodic protection.
Aluminium, Zinc, Magnesium are used as sacrificial anodes.
This method is used for the protection of ships and boats.

Sheets of Mg or Zn are hung around the hull of the ship.
(Fig. 3.11).
Sacrificial zinc or
magnesium
Insulated
Ship hull copper wire
Fig. 3.11 Sacrificial anodic protection of ship
Zn or Mg will act as anode compared to iron (ship or boat is

made of iron), so corrosion concentrates on Zn or Mg. Since they
are sacrificed in the process of saving iron, they are called
sacrificial anodes.
Mg (Sacrificial anode) Sacrificial Zn Insulated wire
or Mg
(a) Underground pipeline (b) Boiler

Fig. 3.12 Sacrificial anodic protection
Important applications of sacrificial anodic protection are
a. Protection of underground pipelines, cables from soil corrosion

(Fig. 3.12(a)).
b. Insertion of Mg sheets into the domestic water boilers to
prevent the formation of rust (Fig. 3.12(b)).
c. Calcium metal is employed to minimize engine corrosion.
3.5.2 Impressed Current Cathodic Protection Method
In this method, an impressed current is applied in the

opposite direction of the corrosion current to nullify it, and the
corroding metal is converted from anode to cathode.
This can be done by connecting negative terminal
of the battery to the metallic structure to be protected, and
positive terminal of the battery is connected to an inert anode.
Inert anodes used for this purpose are graphite, platinised
titanium. The anode is burried in a “back fill” (containing
mixture of gypsum, coke, breeze, sodium sulphate). The “back
fill” provides good electrical contact to anode (Fig. 3. 13).
Important applications of impressed current cathodic
protection are structures like tanks, pipelines, transmission line
towers, marine piers and laid-up strips, etc.
Source of impressed direct current

Anode Cathode
Graphite
Back fill (anode)
Insulated
copper wire
Buried pipe line-cathode

(protected)
Fig. 3.13 Impressed current cathodic protection
This type of protection is given to underground water pipe

lines, oil pipe lines, ships, etc.
Table 3.2 Comparison of Galvanic method (Sacrificial anode)

and Impressed current cathodic method
Sl. Sacrificial anode method Impressed current method

No
1. No external power supply is External power supply must
necessary. be present.
2. This method requires Here anodes are stable and
periodical replacement of do not disintegrate.
sacrificial anode.
3. Investment is low. Investment is more.
4. Soil and microbiological Soil and microbiological
corrosion effects are not corrosion, corrosion effects
taken into account. are taken into account.
5. This is most economical This method is well suited
method especially when for large structure and long
short-term protection is term operations.
required.
6. This method is suitable But this method can be
when the current practiced even if the current
requirement and the requirement and the
resistivity of the electrolytes resistivity of the electrolyte
are relatively low. are high.
3.5.3 Corrosion Inhibitors

A corrosion inhibitor is a substance which reduces the
corrosion of a metal, when it is added to the corrosive
environment.
Types of Inhibitors
1. Anodic Inhibitors
Examples : Chromates, nitrates, phosphates, tungstates (or) other
ions of transition elements with a high oxygen content.
Anodic inhibitors are those that prevent the corrosion
reaction, occurring at the anode, by forming an insoluble
compound with the newly produced metal ions. These
precipitates are adsorbed on the metal (anode) surface, forming a

protective film and reducing the corrosion rate.
Though this type of control is effective, it may be
dangerous, since sever local attack can occur, if some areas are
uncovered.
2. Cathodic Inhibitors
In an electrochemical corrosion, the cathodic reactions are
of two types depending upon environment.
(a) In An Acidic Solution

Examples : Organic inhibitors heterocyclic nitrogen compounds,
heavy metal soaps.
In an acidic solution, the cathodic reaction is evolution of
hydrogen i.e., like amines, mercaptans, thioureas, substituted
ureas, etc.,
2H+ + 2e H2
The corrosion can be reduced in two ways

(i) By slowing down the diffusion of H+ ions to the cathode. This
can be done by adding organic inhibitors like amines, pyridines,
etc., which are adsorbed at the metal surfaces.
(ii) By Increasing the over voltage of Hydrogen evolution. This
can be done by adding antimony and arsenic oxides which
deposit adherent film of metallic arsenic and antimony at the
cathodic areas.
(b) In a Neutral Solution

Examples :
Sodium sulphite (Na2SO3), hydrazine (N2H4).
In a neutral solution, the cathodic reaction is
- -
H2O + ½O2 + 2e 2OH
The corrosion can be reduced in two ways.
(i) By eliminating the oxygen from the neutral solution, there by

formation of OH- ions are inhibited. This can be done by adding
reducing agents like Na2SO3, N2H4 etc.
(ii) By eliminating the OH- ions from the neutral solution. This
can be done by adding Mg, Zn or Ni salts. These react with OH -
ions form insoluble hydroxides, which are deposited on the
cathode forming less impermeable self - barriers.
3. Vapour Phase Inhibitors (VPI)

Examples : Dicyclohexylammonium nitrate, benzotriazole, etc.
Vapour phase inhibitors (VPI) are organic inhibitors,
which readily vapourise and form a protective layer on the metal
surface. VPI are used in the protection of storage containers,
packing materials, sophisticated equipments, etc.
iv) Control of corrosion by modifying the metal
1. By selection of the metal

Selection of right type of metal is the main factor for corrosion
control. Thus, noble metals are used in ornaments and in surgical
instruments.
2. By using pure metal

Pure metals have higher corrosion resistance. Even a small
amount of impurity may lead to severe corrosion.
3. By alloying
Corrosion resistance of many metals can be improved by
alloying. For example, stainless steel containing chromium
produce a coherent oxide film, which protects the steel from
further attack.
4. By proper design
Some of the important rules for designing, which must be
observed are given below.
i) Avoid galvanic corrosion

If two different metals are joined , galvanic corrosion will occur.
In such a case galvanic corrosion is prevented by
a) Selecting the metals as close as possible in the
electrochemical series.
b) Providing smaller area for cathode and larger area for anode.
Fig
c) Inserting an insulating material between the two metals. (Fig)
ii) Drainage affects corrosion

Tanks and other containers must be designed in such a way that,
the whole of the liquid should be drained off completely. (Fig)
iii) Avoid sharp corners and bends

Sharp corners and bends should always be avoided, and
hence erosion corrosion can be avoided by smooth corners or
curved pipe bends (Fig ).
Fig
iv) by avoiding crevices

Crevices allow moisture and dirt, which results in increased

electrochemical corrosion. This can be prevented by filling the
crevices with a filler (Fig ).
Example : Riveted joints produce crevice corrosion, so welded
joints are preferred.
3.9 PAINTS
Paints are stable mechanical mixtures of one (or) more
pigments.
Paint is a dispersion of pigments in to the drying oil.
The vehicle or drying oil is a film forming material, to
which other ingredients are added in varying amounts.
Requisites (or) Characteristics of a good Paint

It should spread easily on the metal surface.
It should have high covering power.
It should not crack on drying.
It should adhere well to the surface.
The colour of the paint should be stable.
It should be a corrosion and water resistant.
It should give a smooth and pleasing appearance.
It should dry quickly.
Pigment Volume Concentration (P.V.C) of a paint is an

important criterion or a guide for the paint manufacturer to
prepare paints with desired properties.
Generally, the characteristics of paints depends on the

nature and quantities of pigments, extenders and vehicles present
in the paint.
Pigment Volume Concentration (P.V.C)
It is an important property of a paint.
The following equation is used to calculate the P.V.C
Volume of the pigment in the paint

P.V.C =
Volume of the pigment in the paint + Volume
of non-volatile vehicle in the paint.
If the volume of P.V.C increases, the durability, adhesion

and consistency of the paint decreases.
The pigment volume concentration of a paint should be kept

within the limit.
3.9.1 CONSTITUENTS OF PAINTS

The impartant constituents of paints are as follows
1. Pigments 2. Vehicle 3. Drier 4. Thinner
5. Antiskinning agent 6. Plasticizers 7. Filler
Table 3.3 Constituents of Paints and their Functions
Sl. CONSTITU- FUNCTION EXAMPLE

No ENTS
1. Pigments i) To give the White: Pb,TiO2,
desired colour ZnO Blue : Indigo
ii) To cover the Red: Red lead,
manufacturing chrome red.
defects Green: Chromium
iii) To protect oxide, Cr-green
from U-V light Yellow: Cr-yellow,
Cd-yellow
Black: Graphite,
carbon black.
2. Thinner Used to dilute the Turpentine oil,
paints in order to Kerosene, Alcohol
make it easy to
apply on the
surface.
3. Vehicle or It is used to Coconut oil, Linseed
Drying oil dissolve the oil, Castor oil,
pigment Soyabeen oil.
4. Driers They act as Litharge, Oxides of
catalysts and Mn and Co.
increase the rate of
drying process
5. Antiskinning To prevent Polyhydroxy phenol
agent skinning of the
paint.
6. Plasticizers They increase the Triphenyl phosphate,
elasticity of the tributyl phosphate,
film. tertiary amyl alcohol.
7. Fillers They increase the Gypsum, asbestos,
volume of the china clay, talc,
paint reduce the BaSO4
cost.
3.9.2 MECHANISM OF DRYING OF (PAINTS)

DRYING OILS
1. Drying oils are fatty oils which are extracted from seeds.
2. The fatty oils are triesters of glycerol.
3. Formula of fatty oil (Drying oil) is
CH2 COOR2
R1COO CH
CH2 COOR3
where R1, R2, R3, are radicals derived from aliphatic

unsaturated acids (Palmitic acid, Oleic acid)
4. The paint containing these type of drying oils, when exposed

to air becomes a cross-linked polymer by reaction with oxygen
in the atmosphere.
5. In general, oils containing fatty acids having conjugated

double bonds dry faster than those that have non-conjugated
double bonds.
6. The mechanism of drying oils has not been completely

understood. However, according to acceptable mechanism, the
following points are given
i) The oil combine with oxygen to form peroxides.
ii) The film takes of oxygen continuously and decomposes.
iii) The peroxy radicals combine to give cross-linked
polyperoxides which are stable.
iv) These polyperoxides are decomposed by light and heat to
form other linkages.
Mechanism
1. The oil after application to the surface it becomes solidifies. It

is said to “dry up”. Hence it is called as “drying oil”.
2. These oils contain unsaturated esters.
3. The double bonds in them absorb oxygen from the air and
form peroxides (with 0 - 0) linkages first and these linkages react
with adjacent chain unsaturation centres and form cross links.
O2
C=C C-C
O-O
C-C C-C
O-O
C=C C-C
These cross links when continued sufficiently solidify the

liquid oil. This is only one of the mechanisms that is possible.
Generally, the more the unsaturation centres (carbon -

carbon double bonds) the more is the capacity for O 2 absorption
and quick “drying” (or) solidification.
3.9.3 SPECIAL PAINTS

Apart from being used for protection from corrosive
atmospheres, for decoration, for reflecting away heat etc., paints
have been formulated for special purposes (or) uses are called as
special paints.
Some of the important special paints are as follows
(i) Fire Retardant Paints

These paints contains ingredients like calcium ammonium
phosphate, magnesium ammonium phosphate, calcium carbonate
etc.,
Under intense heat, they decompose to give CO2, NH3,
H2O for these gases (non - inflammable gases) cover the flame
quickly and extinguish the fire.
Uses
This is mainly used in wooden houses.
(ii) Temperature Indicating Paints

This paint contain ingredients like amine salts of copper,
iron, manganese, cobalt and nickel.
These substances undergo colour changes and indicating a
particular temperature.
Uses
Used in the outerwalls of the reactors and furnaces to
indicate the temperature by its colour change.
(iii) Water Repellant Paints
This paints consists of silicones which is dissolved in

suitable solvent with required amount of pigments.
Paints containing asphalt or bitumens are also used for
water proofing.
Uses
Used in ships, boats and marine equipments.
(iii) thicker oxide coating and hence it is more protective
3.6 PROTECTIVE COATINGS

Introduction
Protective coatings are used to protect the metals from
corrosion. Protective coatings act as a physical barrier between
the coated metal surface and the environment. However they are
also used for the decorative purpose. In addition to corrosion
protection and decoration, they import some special properties
such as hardness, electrical properties, oxidation-resistance and
thermal insulating properties to the protected surface.
Coatings like paints, varnishes, lacquers and enamels are

called organic coatings. They are applied on the metallic surfaces
for both corrosion resistant and decoration.
Classification
Protective coatings
Inorganic coatings Organic coatings
Metallic coatings Non-metallic

coatings
1. Hot dipping 1. Surface (or) chemical 1. Paints

(a) Galvanising conversion coating 2. Varnishes
(b) Tinning 3. Lacquers
(a) Chromate coating 4. Enamels
2. Metal cladding (b) Phosphate coating
(c) Oxide coating
3. Cementation
(a) Sherardising 2. Anodising
(b) Chromising 3. Vitreous or porcelain
(c) Calorising enamel coating
4. Electroplating
3.7 PRE-TREATMENT OF METAL SURFACE
The base metal surface is usually contaminated with rust,

scale, oil, grease etc. If they are present at the time of coating, it
will give porous and discontinuous coatings. Therefore inorder to
get a uniform and smooth protective coatings, these substances
should be removed by proper pretreatment methods. This is
called as pre-treatment of metal surface.
They are
(i) Mechanical Method

These methods are useful to remove loose scale and
oxides. The various methods are hammering, scraping, wire -
brushing and sand blasting etc. Sand blasting is done when a
slightly roughened surface is desired. It is the process in which
sand or abrasives along with air steam under pressure of 25-100
atm is concentrated on the metal surface.
(ii) Chemical Method

These methods are mainly used for removing oils, grease,
rust etc.,
a) Solvent Cleaning
Solvents such as alcohols, xylene, toluene, chlorinated
hydrocarbons etc., are generally used in solvent cleaning. This is
followed by cleaning with steam and hot water containing
wetting agents.
b) Alkali Cleaning
In alkali cleaning chemicals like sodium hydroxide,
tri sodiumphosphate, sodium silicate, soda ash etc., are used. This
is useful in removing oil paints. This cleaning is followed by
washing with 1% chromic acid solution.
c) Acid Pickling
Acids like H2SO4, HCl, HF, H3PO4 and HNO3 in dilute
solutions are used for ferrous metals. For non-ferrous metals
HNO3 with other acids is mainly used. The metals are dipped in
side the solution at a higher temperature.
(iii) Electrochemical method

This method is used where the oxide scales cannot be
removed by the other methods. The metal whose surface has to
be cleaned is made either anode (Cathode pickling) or cathode
(Anode pickling). The electrolyte is usually in acid solution or an
alkali solution on passing a direct current, the dissolution of the

oxide scales at anode or cathode takes place.
3.8 ELECTROPLATING (or)

ELECTRO DEPOSITION
(I) Principle
Electroplating is the process in which the coating metal is
deposited on the base metal by passing a direct current through
an electrolytic solution containing the soluble salt of the coating
metal.
The base metal to be plated is made cathode of an
electrolytic cell, whereas the anode is either made of the coating
metal itself or an inert material of good electrical conductivity.
Anode
( Coat Metal )
Cathode
( Base Metal )
Electrolyte
Fig. : 3.14 Electro plating
Example :
Graphite.
Objectives
1. On Metals
(i) To increase the resistance to corrosion of the coated metal.
(ii) To improve the hardness and physical appearance of the
article.
(iii) To increase the decorative and commercial values of the
article.
(iv) To increase resistance to chemical attack.
(v) To improve the properties of the surface of the article.
2. On Non-metals
(i) To increase strength
(ii) To preserve and decorate the surfaces of non-metals like
plastics, wood, glass, etc.,
(iii) For making the surface conductivity by utilization of light
weight, non-metallic materials.
(II) Theory
Suppose the anode is made of coating metal in the
electrolytic cell. During electrolysis, the concentration of
electrolytic bath remains unaltered, since the metal ions deposited
from the bath on cathode are replenished continuously by the
reaction of free anions with the anode.
Example : If CuSO4 solution is used as an electrolyte, it ionises
as
CuSO4 Cu2+ + SO2-4
on passing current, Cu2+ ions go to the cathode and get deposited
there.
-
Cu2+ + 2e Cu (at cathode)
The free sulphate ions migrate to the copper anode and
dissolve an equivalent amount of copper to form CuSO 4.
SO2-4 + Cu CuSO4 + 2e- (at anode)
The copper sulphate formed gets dissolved in the
electrolyte. Thus, there is a continuous replenishment of
electrolyte during electrolysis.
(III) Process
The article to be plated is first treated with dil. HCl (or)
dil. H2SO4 to clean the surface. The cleaned article is then made
cathode of an electrolytic cell. The anode is either the coating
metal itself (or) an inert material of good electrical conductivity.
When direct current is passed from a battery, coating

metal ions migrate to the cathode and get deposited there. Thus, a
thin layer of coating-metal is obtained on the article (at cathode).
In order to get strong, adherent and smooth deposit certain
additives (glue, gelatin, etc.,) are added to the electrolytic bath. In
order to improve the brightness of deposit, brightening agents are
added in the electrolytic bath. The favourable conditions for a
good electro deposit are optimum temperature, optimum current
density and low metal ion concentrations.
Characteristics of Various Plating
1. Nickel Plating
(i) It gives hard, adherent and good wear-resistant surface.
(ii) It is used as an undercoat for articles, which are finally to be
chromium-plated.
2. Chromium Coating
(i) It is porous and somewhat non-adherent.
(ii) The articles are first given an undercoat of copper or
nickel, before chromium plating.
3. Copper plating
(i) It is an under coat for Ni-Cr electro deposit for smoothening

out the irregularities.
(ii) It is used as a protective coating for steel article.
(iii)It is coated at the bottom of stainless steel cooking utensils to
effect better heat transfer.
Fig Copper plating
Consider a iron cup is plated by copper metal.

For copper plating Cu metal is made as anode the iron cup is
made as cathode and the CuSO4 solution is used as electrolyte.
When electric current is passed through the electrolyte, Cu 2+ in
the electrolyte deposit on the iron cup. Thus copper is coated on
the iron cup.
4. Gold Plating
(i)The deposits of gold are used for electrical and electronic
applications.
(ii) It is used for high quality decorations and high oxidation
resistant coatings.
(iii)For jewellery very thin coating is given (0.05 - 1.0 microns).
Electroplating (Au)
Electroless plating(Ni)
Electroless plating is a technique of depositing a noble metal

(from its salt solution) on a catalically active surface of a less
noble metal by employing a suitable reducing agent without
using electrical energy.
The added reducing agent causes the reduction of the metallic

ions to metal which eventually gets plated over the catalically
activated surface giving a highly uniform, but thin coating.
Thus
Metal ions + reducing agent Metal + Oixdized product(s)
Deposited over
Catalycally active
surface
The driving force is autocatalytic redox reaction on pretreated

catalytic surface. Various aspects of electroless plating are:
1. Preparation of active surface of the object to be plated.

This step is most important in this technique. This is achieved by
using one of the following methods:
i) Etching i.e. by acid treatment
ii) Electroplating a thin layer of the metal to be plated or any
other suitable metal. This is usually followed by heat treatment.
iii) Treating with stannous chloride, followed by dipping in

palladium chloride solution. This treatment yields a thin layer of
Pd on the treated surface. Usually, this is followed in case of
plastic and printed circuit board.
2. Plating bath is composed of :

i) Soluble slat of metal ( like chloride or sulphate) to be plated.
ii) Reducing agent like formaldehyde, hypophosphite etc.,
iii) Complexing agent like Tartarate , Citrate, succinate etc.
This improves the quality of the deposit.
iv) Exaltant like succinate, fluoride, glycinate etc.
This enhances the plating rate.
v) Stabilizer like Thio-urea, cations of lead, calcium, Thalium
etc., is added to prevent the deposition of plating bath solution.
vi) Buffer like sodium acetate, sodium hydroxide plus rochelle

salt, etc is added to control the pH of the bath. It may be pointed
that pH of the bath plays a critical role in getting a uniform, but
thin deposit.
Advantages of electroless plating over electroplating

1. No electrical energy is required.
2 Better throwing power.
3. Plating on articles made of insulators(like plastics) and
semiconductors can easily be carried out.
4. Even intricate parts of (irregular shapes ) can be plated
uniformly.
5. Electroless plated coatings possess unique mechanical,
chemical and magnetic features.
Electroless Nickel plating

Electroless Nickel plating involves the following features:
Pretreatment and activation of the surface

The surface to be plated is first degreased (by using organic

solvents or alkali), followed by acid-treatment.
a) Metals and alloys like Al, Cu , Fe, brass, etc. be directly nickel
plated without any activation.
b) Stainless steel surface is activated by dipping in hot solution of

50% dilute H2SO4.
c) Activation of Mg alloy surface is carried out by giving a thin
coating of Zn and Cu over it.
d) Activation of
Table 3.8 Differences between Electroplating and Anodising
3.17.3 Hot Dipping Method :

1. It is one of the most familiar method.
2.It is the very simple process.
3.It give good results.
4.In this method the base metal is dipped in a molten coat metal,
for a particular time to get the uniform coatings.
5.The condition for succesful hot dipping methods are

(i) The coat metal having lower melting point than the base
metal.
(ii) The coat metal must form an alloy with the base metal.
(iii) The base metal should with stand the high temperature of
dipping without any change in properties.
(iv) Hot dipping is done on Fe with Zn, Sn and Al as coating

metal.
The common examples of hot dipping are

1. Galvanising
2. Tinning
1. Galvanising :
It is a process of coating zinc over iron sheet (base metal),
Process : The base metal iron sheet is first pickled (pre-
treatment) with dil. H2SO4 to remove any oxide coating present. It
is then thoroughly washed with water. The cleaned dried iron
sheet is dipped in a bath of molten zinc (coating metal) which is
kept at 425 - 430OC. The surface of the molten coating metal is
covered with NH4Cl flux to prevent the oxidation of molten
coating metal to its oxide. (Fig. 3.18)
Pair of hot
Steel Sheet rollers
Drying Galvanised Steel
Hot air Amm. Chloride flux
Dil. H2SO4 Water Molten zinc

(Pickling) (washing) at 425 - 430OC
Fig 3.18 : Galvanising of Steel
Due to the formation of a thin layer of an inter metallic

compound (Fe3Zn10 or FeZn or FeZn13) at the interphase (base
metal), a pure layer of zinc is tightly adhered to the iron sheet.
The excess coating metal from the iron sheet is removed by
passing through a pair of hot rollers.
Uses : Galvanised iron is used in automobile underbody parts,

roofing sheet, lamp posts, etc.
2. Tinning :
It is a process of coating tin over iron sheet (base metal).
Process : The base metal is first pickled with dilute sulphuric acid
to remove any oxide film present. It is then washed with water.
The cleaned, dried base metal is dipped in a bath of molten tin
which is kept at 230 - 235OC. The surface of molten coating
metal is covered with ZnCl2 flux to clean the base metal further.
In this process, palm oil is used to prevent the oxidation of
molten coating metal (tin) to its oxide (Fig. 3.19).
Pair of hot
Steel Sheet rollers
Tinned Steet
ZnCl2
Flux
Dil. H2SO4 Molten tin Palm Oil

(Pickling) 230 - 235OC
Fig 3.19 : Tinning of Steel
Due to the formation of a thin layer of Fe-Sn alloy

(FeSn2) at the inter phase (base metal), a pure layer of tin is
tightly adhered to the iron sheet. The excess coating metal from
the iron sheet is removed by passing through a pair of hot rollers.
Uses : Tin-plated iron is used in food containers because of its

non-toxic nature.
Table 3.9 Differences between electroplating and hot dipping
QUESTIONS :
1. What are the important constituents of a paint? Explain

the function of the various constituents.
[BU. Nov ‘94, ‘95, ‘96, Apr ‘97; MSU. Apr, ‘97]
2. Bring out the similarities and dissimilarities in the

electroplating and anodizing techniques. Give the application of
the two.
[BU. Nov, ‘94.]
3. Distinguish the various organic coating from one another.

[MSU.Nov, ‘94]
4. How the hot dip process is carried our ?

[MSU. Nov, ‘94; MKU.Nov, ‘95, ‘96; Apr,’97.]
5. Describe the various features of anodizing of aluminium.
6. Describe the mechanisms of drying of an oil paint.

[BDU - Nov.‘95; Apr, ‘97; BU - Apr. ‘96; Mds - Apr. ‘99]
7. Write a note on surface preparation for metallic coating.

[BDU - Nov. ‘95; MKU - Nov. ‘95; Apr. ‘97; BU - Apr. ‘96]
8. Write a short note on various special paints.

[MSU-Apr. ‘95, Nov. ‘96; BU - Apr. ‘96, Apr. ‘97; Mds Oct. 98]
9. What are the main objectives of electroplanting. Give an

account of the method used in electroplating of nickel on steel.
[Mds - Oct. ‘96, Apr. ‘99]
10. Discuss any two types of metallic coatings. [MKU - Apr. ‘95]
11. Write notes on : (i) Lacquers [MKU - Nov. ‘96]

12.Write briefly on (i) Types of varnish and their utility (ii)
Anodising. [Mds - Oct. ‘97; BU - Apr. ‘96; MSU - Apr. ‘96]
13. How are galvanizing and tinning are carried out? Bring out
the differences.
[BU - Nov. ‘95; MSU- Apr. ‘95, No. ‘96; MDS -Apr. ‘98]
14. What are surface conversion processes ? How do they prevent

corrosion ? [BU - Nov. ‘95]
15. What are the constituents present in paint, varnish and

lacquer? Mention their special qualities and uses ?
[Mds - Apr. ‘98]
16. What is electrode potential ?
17.Write the definitions of single electrode potential and standard

electrode potential?
18.What is electrochemical series ? Give its significance.

Unit - Ii Corrosion and Corrosion Control

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Corrosion and Corrosion control 3.

Now a days it is necessary to pay more attention to

Example : Fe2O3, ZnO, PbS, CaCO3, etc.,

3.2 CLASSIFICATION OF CORROSION

The corrosion process is classified on the basis of

3.2.1 Dry Corrosion (or) Chemical Corrosion

This can be classified as follows,

(1) Corrosion by oxygen (Oxidation corrosion)

Fig : 3.1 Oxidation corrosion

Oxidation first occurs at the surface of the metal resulting

Oxygen is converted to oxygen ion (O2-)

M + ½O2 M2+ + O2- MO (Metal Oxide)

Nature of the metal oxide films formed

There are generally four types of metal oxide films are

(i) Stable film

(ii) Unstable film

(iii) Porous film

(iv) Volatile film

Pilling - Bed Worth rule

(i) Stable film

(ii) Unstable film

(iii) Porous film

(iv) Volatile film

Pilling - Bed Worth rule

Protective layer metals e.g., Al, Sn, Pb, Cu, etc,.

b) Corrosion by other gases

Cl2 + 2Ag 2AgCl

3.Metals combines with H2S gas to liberate atomic hydrogen.

The atomic hydrogen is very reactive and penetrate the

The atomic hydrogen recombines inside the metal and

4.Atomic hydrogen are formed by dissociation of H 2 gas at high

5. The atomic hydrogen is highly reactive and combine with

c) Liquid metal corrosion

3.2.2 Wet Corrosion (or)

In the above condition one part of the metal becomes

(i) Hydrogen evolution mechanism

This can be explained as follows,

(i) Hydrogen evolution mechanism

In this type of corrosion, anodes possess large surface

Anodic solution (electrolyte)

Fig : 3.2 Hydrogen Evolution

(ii) Oxygen Absorption mechanism

Fig : 3.3 Oxygen Absorption

The liberated electrons flows from the anode to the

If enough oxygen is present, ferrous hydroxide is

Table 3.1 Differences Between Chemical and Electro

3.2.3 Galvanic Corrosion

Fig : 3.4 Galvanic corrosion (Zn / Fe)

At cathode : ½O2 + H2O + 2e 2OH (Reduction)

Overall : Zn + ½O2 + H2O Zn2+ + 2OH Zn(OH)2

Fig : 3.5 Galvanic corrosion (Fe / Cu)

At cathode : ½O2 + H2O + 2e 2OH

Overall : Fe + ½O2 + H2O Fe2+ + 2OH Fe(OH)2

The galvanic corrosion can be avoided by

1. Coupling of metals very close in the emf series.

3.2.4 Concentration Cell Corrosion (or)

Electrolyte Less oxygenated

Fig. : 3.6 Concentration cell corrosion (Metal / Electrolyte)