UNIT-3 Corrosion and its Control

Introduction
A continuous deterioration or degradation of metal due to their reactions with its
environmental gases and other substances is called as Corrosion. It leads to a
change in physical properties of the metal. Corrosion causes weakening of a material
due to breaking of metal surface and shattering. In the field of engineering metals are
generally used as fabrication or construction materials. The metal structures
deteriorate if they are not properly maintained.

Definition
"Corrosion is the gradual destruction or deterioration of metals or alloys by the
chemical or electrochemical reaction with its environment"

Causes of Corrosion
Metals occur in two different forms.
1. The native state.
2. The combined state.
Native state
An element is said to exist in the native state when it is in its elementary form.
They occur in an uncombined state which is non–reactive towards the environment.
Noble metals are good examples that exist as such in the earth’s crust. They posses
very good corrosion resistance and are less reactive, elements such as gold,
platinum, etc., are found to be in the native state.

Combined State
An element is said to exist in the combined state when it exists in nature as a
compound. Reactive elements occur in nature in the combined state. Expect noble
metals, all other metals are reactive and react with environment to form a stable
compound as their oxides or sulphides or chlorides or carbonates. They exist in the
form of stable compounds called ores and minerals. A good example is, when iron is
exposed to air that is moist it gets corroded and a layer of reddish-brown substance
called as rust is formed on the surface. Rust is a chemically hydrated form of iron (III)
oxide, Fe2O3. xH2O. Copper metal when exposed to moist air gets coated forming a
greenish white powdery substance which is copper carbonate.

How does corrosion occur?

A metal is extracted from its metallic compound or ore. During the extraction an
ore is reduced to its metallic state by applying energy in the form of various
processes. When a metal exists in its pure metallic state it is highly unstable. It is
considered to be in a high energy state or excited state. So, when a metal is extracted
from their ore the reverse process begins and form metallic compound which reaches
the lower energy state or it is said to be thermodynamically stable. When a metal is
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used in various forms they are exposed to different environments. Here the metallic
surface starts to decay or get converted to a more stable compound.

Corrosion - Oxidation
Metal Metallic Compound + Energy
Metallurgy -Reduction

Corroded metals are thermodynamically more stable than pure metals but due to
corrosion, useful properties like malleability, ductility, hardness, luster and electrical
conductivity are lost.

Effects of corrosion
Some effects of corrosion are
 It reduces the metal thickness which leads to a loss of mechanical strength and
structural failure.
 Corrosion is hazardous and creates injuries to people arising from structural.
 Cost of the product is reduced due to deterioration of appearance.
 Blockage of pipes due to solid corrosion products.
 Expense of equipment replacement is high.
 Plant failure occurs.

Classification or theories of corrosion

Based on the environment, corrosion is classified into
 Dry or Chemical corrosion.
 Wet or Electrochemical corrosion.

Dry or Chemical Corrosion

Dry corrosion is due to the attack of metal surfaces by the atmospheric gases
such as oxygen, hydrogen sulphide, sulphur dioxide, nitrogen, etc.,
There are 3 main types of dry corrosion.
1. Oxidation corrosion (or) corrosion by oxygen.
2. Corrosion by hydrogen
3. Liquid–metal corrosion.

Oxidation corrosion (or) corrosion by oxygen

Oxidation corrosion occurs when there is a direct action of oxygen at low or
high temperature on metals in the absence of moisture. At normal temperature there
is a slight attack on the metal. But alkalies and alkaline earth metals are rapidly
oxidized at low temperature and almost all metals except the noble metals are
oxidized at high temperatures.
Reactions in oxidation corrosion
2M → 2Mn+ + 2ne- (Loss of electrons)
n/2 02 +2ne- → n02- (Gain of electrons)

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Overall reaction
2M + n/2O2 → 2Mn+ + nO2- (Metal oxide)
Mechanism
Oxidation first occurs at the surface of the metal and the resulting metal oxide
forms a barrier which restricts further oxidation. For oxidation to continue the metal
must diffuse outwards through the metal oxide layer or oxygen must diffuse inwards
through the scale to the underlying metal. The outward diffusion of the metal is more
rapid than inward diffusion of oxygen, since the metal ion is much smaller than
oxygen molecule, thus there is higher mobility. (Fig. 3.1.)

Fig.3.1. Mechanism and photographic image of oxidation corrosion

Nature of oxide film

There are three types of oxide film formed on the metal surface
 Stable oxide layer
A stable oxide layer is a fine-grained structure which gets adsorbed tight on to
the metal surface. Such a layer is highly impervious in nature and stops further
oxygen attack through diffusion. Such a film behaves as a protective coating and no
further corrosion can develop.
Example: Oxides of Cu, Al, Sn, Pb, etc.,
 Unstable oxide layer
Unstable oxide layer is produced on to the surface of the noble metals, which
decomposes back into metal and oxygen.
Metal oxide Metal + Oxygen
Example: Oxides of Pt, Ag, etc.,
 Volatile oxide layer
The oxide layer volatilizes or forms a gas and disappears immediately after it is
formed, which causes further corrosion.
Example: Molybdenum oxide (MoO3) is volatile.

Pilling–Bedworth ratio
The Pilling-Bedworth ratio or P-B ratio is the ratio of the volume of the metal
oxide formed to the volume of the metal consumed. On the basis of the Pilling

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bedworth ratio a metal can be judged whether it is likely to form a protective oxide
layer.
 Porous (or) Non–protective oxide film
If the volume of the oxide layer formed is less than the volume of the metal
consumed, the oxide layer is considered to be porous and non–protective. A good
example is alkali and alkaline earth metals such as Na, Ca, etc.
 Non - Porous (or) Protective oxide film
If the volume of the oxide layer formed is greater than the volume of the metal
consumed, the oxide layer is considered to be non–porous and protective. The oxides
of heavy metals such as Pb, Sn, are good examples.

Corrosion by hydrogen
 Hydrogen embrittlement
Hydrogen embrittlement is a process by which various metals
become brittleand fracture on exposure to hydrogen. Hydrogen embrittlement is the
introduction of hydrogen into metals forming cracks in the metal.
When a metal such as Fe react with H2S at ordinary temperature it causes the
formation of atomic hydrogen.
Fe + H2S → FeS + 2H
This atomic hydrogen diffuses into the metal immediately and recombines to
form molecular hydrogen.
H + H → H2 
These molecular hydrogen gas formed penetrates into the voids present and
develops a high pressure which causes cracks and blisters on metal. (Fig.3.2.)

Fig.3.2. Mechanism and Photographic image of Hydrogen embrittlement

 Decarburization (at higher temperature)

When steel is exposed to hydrogen at very high temperatures hydrogen
penetrates into the alloy and combines with carbon to form tiny packets
of methane in the internal surfaces. This methane does not diffuse out of the metal
but gets collects in the voids at high pressure leading to cracks in the steel.

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This process leads to decarburization of the steel which results in loss of strength
and ductility of steel.
H 2 Heat

 2H
When steel is exposed to hydrogen environment atomic hydrogen readily
combines with the carbon present in steel to produce methane gas.
C  4H 
 CH 4 
Liquid–metal corrosion
Liquid metal corrosion also called as liquid metal embrittlement is caused
when a certain metal undergoes fracture when it is introduced into a liquid metals
environment. For example when liquid gallium is introduced on an aluminium sheet
liquid metal embrittlement is observed. During liquid metal embrittlement cracking
occurs drastically leading to very high crack growth rates. These effects are seen even
in solid alloys when one of the metals is brought close to its melting point. For
example cadmium when operated at high temperature leads to solid metal
embrittlement. Embrittlement caused due to mercury spills cause corrosion.
(Fig.3.4.)

Fig.3.4. Photographic image of Liquid–metal corrosion

Wet or Electro–Chemical Corrosion

Mechanism of wet corrosion

Wet corrosion of a metal takes place through electron transfer which involves
both oxidation and reduction. During oxidation a metal atom loses electrons and the
surrounding environment undergoes reduction and gains electrons. The metal in
which there is loss of electrons is called as the anode and the other metal or liquid or
gas that gains electrons is called the cathode.
The reaction is as follows
At anode
At the anode oxidation or dissolution of the metal occurs
M
 M 2  2e

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At cathode
At the cathode reduction of the solid or liquid or gas occurs. This depends on
the nature of the environment. There are two types of environment and they are

a. Acidic environment or Hydrogen evolution type corrosion

The metals that possessa anodic potential in the electrochemical series have got
a tendency to get dissolved in acidic solution with the evolution of hydrogen gas (Fig.
3.5.)

Fig. 3.5. Hydrogen evolution type corrosion

For example when iron metal contacts with non–oxidizing acid like H2SO4
and HCl, H2 evolution occurs.
At anode
Iron undergoes dissolution to give Fe2+ ions with the liberation of electrons.
Fe 
 Fe2  2e (Oxidation)
At cathode
The liberated electrons flow from anodic to cathodic part, where H– ions get
reduced to H2.
2H  2e 
 H2  (reduction)
b. Neutral environment or Absorption of oxygen or Formation of hydroxide ion
type corrosion
If the corrosive environment is slightly alkaline or neutral. The product formed is
at the cathode that is hydroxide ions are formed at the cathode.
½O2 + 2e–+H2O   2OH–
The metal ions from the anode and the non–metallic ions from the cathode diffuse
towards each other through a conducting medium to form a corrosion product
between the anode and the cathode. For example when iron is in contact with an
electrolyte in presence of oxygen, OH– ions are formed. A thin film of iron oxide is
coated on the surface. However, if the oxide film develops crack at the anode created
on the surface while the remaining part acts as cathode. (Fig. 3.6.)
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 Fig. 3.6. Absorption of oxygen type corrosion
At anode
Iron dissolves as Fe2+ with the liberation of electrons.
Fe  Fe2  2e (oxidation)
At cathode
The liberated electrons flow from anodic to cathodic part through metal, where
the electrons are taken up by the dissolved oxygen to form OH– ions.
½O2 + H2O + 2e–   2OH–
Thus the net corrosion reaction is
Fe2  2OH  
 Fe(OH)2 
If enough O2 is present Fe(OH)2 is easily oxidized to Fe(OH)3, a rust (Fe2O3, H2O).
4Fe(OH)2  O2  2H2O 
 4Fe(OH)3

Table 3.1 Difference between Chemical and Electro chemical Corrosion

S.No. Chemical Corrosion Electrochemical Corrosion
1. It occurs only in dry condition. It occurs in presence of water or
electrolyte.
2. It is due to the attack of the metal It is due to the set-up of a large number of
on the environment. cathodic and anodic areas.
3. Even a homogeneous metal Heterogeneous surface (or) Bimetallic
surface gets corroded. contact is the condition.
4. Corrosion products accumulate Corrosion occurs at the anode, while
where corrosion occurs. products formed elsewhere.
5. Chemical corrosion is self– Electrochemical corrosion is continuous
controlled process.
6. It follows adsorption mechanism It follows electrochemical reaction.
Example: Formation of mild scale Example: Rusting of iron in moist
on iron surface atmosphere.

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Types of electrochemical corrosion
1. Galvanic corrosion
When two different metallic materials are connected galvanic corrosion occurs.
The material that is more anodic will corrode.
The corrosion rate depends strongly on
 The electric conductivity of the environment (Electrolyte or solution)
 The difference in corrosion potential between the galvanically coupled
materials
 The surface ratio between the electrodes.
For example, when stainless steel is joined with steel, stainless tubes and
carbon-steel tube plates in a heat exchanger, the carbon steel suffers from galvanic
corrosion attack. When stainless steel is combined with graphite, the attack will be
on steel. Graphite gaskets should therefore be avoided.
Here, the metal with more negative electrode potential according to the
electrochemical series acts as anode and the metal with less negative electrode
potential acts as cathode. (Fig.3.7.)

Fig.3.7. Mechanism and Photographic image of Galvanic corrosion

Fig. 3.9 (a) represents Zn–Fe couple, in which zinc is more active since it has a
position that is higher in the emf series. Dissolves in preference to iron which is a
less active metal i.e., Zn acts as anode and undergoes corrosion and Fe acts as
cathode.
Fig. 3.9 (b) represents Fe–Cu couple, in which iron is more active when
compared to Cu dissolves in preference to copper is less active i.e., Fe acts as anode
and undergoes corrosion and Cu acts as cathode.
Examples for Galvanic Corrosion
 Steel screw in a brass marine hardware corrodes
Due to galvanic corrosion, Iron which has a higher position in electrochemical
series becomes an anode and gets corroded, while brass which is lower in
electrochemical series acts as cathode and is not attacked.

 Bolt and Nut made of the same metal is preferred

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 To avoid galvanic corrosion, it is made up of the same metal so it has no anodic
and cathodic part.
Prevention
Galvanic corrosion can be reduced by insulating between the two metals.

2. Differential aeration (or) concentration cell corrosion

Corrosion of metals due to the uneven supply of air on the metal surface is
known as differential aerations corrosion. It is caused when metals are exposed to
different concentrations of oxygen or any electrolyte on the surface of the base metal.
The part of the metal exposed to high concentration of oxygen acts as a cathode and
part of the metal exposed to low concentration of oxygen acts as anode. Hence, the
region that is less oxygenated undergoes corrosion.
A good example is a motor pump where the metal pipe is partially immersed in water
or a conducting solution, it is also called water line corrosion.

Fig. 3.8. Differential aeration corrosion

If a metal is immersed partially into a solution, (Fig. 3.8.) the part of the metal above
the solution is considered to be more aerated and hence become cathodic. On the
other hand, the part of the metal inside the solution is considered to be less aerated
and thus, become anodic and suffers corrosion.
At anode (less aerated) corrosion occurs
M
 M 2  2e
At cathode (more aerated part) OH– ions are produced.
½O2 + H2O + 2e–   2OH–
Examples for Differential aeration corrosion
a. Pitting or localized corrosion
b. Crevice corrosion.
c. Pipeline corrosion
d. Corrosion on wire fence.

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a. Pitting corrosion
Pitting corrosion occurs in an area where there is a formation of a hole and the
area around the metal is unattacked.

Fig. 3.9. Pitting corrosion

Example: drop of water, sand, dust, scale, etc. on a metal.
Consider a railway track during a rainy day, a drop of water or aqueous solution
falls on the metal surface (Fig. 3.9). The area below the drop of water acts as an
anode since there is less oxygen concentration. This area suffers corrosion. The area
that is freely exposed to air acts as a cathode, due to high oxygen concentration.
The rate of corrosion will be more where the area of cathode is larger and the
area of anode is smaller. Therefore, more and more material are removed from the
same spot. Thus, a small hole or pit is formed on the surface of the metal so it is
called as pitting corrosion.
At anode
At the anode, Iron is oxidized to Fe2+ ions.
Fe → Fe2+ + 2e–
At cathode
At the cathode, oxygen is converted to OH– ions.
½O2 + H2O + 2e–→ 2OH–
Net reaction is
Fe2+ + 2OH–→ Fe(OH)2 → Fe(OH)3
b. Crevice corrosion
Crevice corrosion occurs in places where small volumes of solutions that are
stagnant below seals or in crevices, a good example is a nut and rivet head. Deposits
of dust, sand and corrosion products which cannot be removed can also lead to
crevice corrosion. It is seen particularly in metals which are unstable in the presence
of high Cl- and H+ ions concentrations.
Crevice corrosion takes place when alloys are exposed to a chloride rich media
gradual acidification take place inside the crevice that leads to corrosion. Galvanic
corrosion does not occur when crevice corrosion occurs. (Fig. 3.10.)

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Fig.3.10. Mechanism and Photographic image of crevice corrosion

c. Pipeline corrosion

Fig. 3.11. Pipeline corrosion

Differential aeration corrosion may also occur in different parts of pipeline.
Buried pipelines or cables passing through the soil, from one type of soil to
another say, from clay that is less aerated to sand that is more aerated may get
corroded due to differential aeration.(Fig. 3.11.)
d. Corrosion on a wire fence
Corrosion on a wire fence occurs in areas where the wires inter cross with one
another. This area seems to be less aerated and acts as an anode. The rest of the
fence acts as a cathode. The part that acts as an anode results in corrosion.( Fig.
3.12.)

Fig.3.12. Mechanism and Photographic image of corrosion on a wire fence

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Other examples for differential aeration corrosion
 Corrosion occurring under metal washers, where oxygen cannot diffuse easily.
 Lead pipeline passing through clay to cinders undergo corrosion. Since the
pipeline under cinders is more aerated, it gets corroded easily.

FACTORS INFLUENCING THE RATE OF CORROSION

The rate and extent of corrosion mainly depends on
1. Nature of the metal.
2. Nature of the environment.

 Nature of the metal

a. Position in emf series
Position of the metal in the emf series plays a major role in the extent of
corrosion. All metals in the anodic region above hydrogen in emf series have a
tendency to get corroded. Lower the reduction potential of the metal the greater is the
rate of corrosion. When two metals are in electrical contact metal that has high
negative reduction potential undergoes corrosion. So, the rate of corrosion depends
on the difference in position in the electrochemical series. Greater the difference
higher is the corrosion rate.

b. Relative areas of the anode and cathode

The rate of corrosion increases when the cathodic area is high. When the area
of the cathode is high the demand for electrons is also high which increases the rate
of corrosion.

c. Purity of the metal

Pure metals will not corrode. The presence of impurities in a metal creates
heterogeneity and thus acts like a galvanic cell. It sets up a distinct anode and
cathode in the metal. Higher the amount of impurity greater is the rate of corrosion
at the anode.
The effect of impurities on the rate of corrosion of zinc is given below.
% purity of zinc 99.999 99.99 99.95
Corrosion rate 1 2650 5000

d. Over voltage or over potential

The over voltage of a metal plays an important role in corrosion. Since over
voltage of the corrosive environment is inversely proportional to corrosion rate. For
example, the normal hydrogen over voltage of zinc metal when it dipped in 1 M H2SO4
is 0.7 volt. Here the rate of corrosion is very low. By adding small amount of
impurity like CuSO4 to H2SO4, the hydrogen over voltage goes down to 0.33 V. This
results in the corrosion of zinc metal.

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e. Nature of the surface film
The nature of the oxide film formed on the metal surface decides the extent of
corrosion which can be decided by Pilling – Bedworth rule
i. In the case of alkaline earth metals such as Na, Ca, and alkali metals from
oxide, whose volume is less than the volume of the metal. Hence the oxide
film will be porous and bring about further corrosion.
ii. But in heavy metals Al, Cr, etc., form oxide, whose volume is greater than
that of the metal. Hence the oxide film will be non–porous and prevents
further corrosion.

f. Nature of the corrosion product

If the corrosion product dissolves in the medium the corrosion rate is faster.
Similarly, if the corrosion product is volatile (like MoO3 on Mo surface), the corrosion
rate will be faster.

 Nature of the environment

a. Temperature
Temperature plays a major role in corrosion since it is directly proportional to
the rate of corrosion. The rate of a chemical reaction and formation of the product
increases with increase in temperature. So, the corrosion rate increases with
temperature.

b. Humidity
Corrosion rate increases when the rate of humidity increases in the
environment. Moisture is a good solvent for oxygen to produce the electrolyte. This is
required for a corrosion cell.

c. Presence of corrosive gases

The acidic gases like, CO2, SO2, H2S and fumes of HCl, H2SO4, etc., produce
electrolytes, which are acidic and increases the electrochemical corrosion.

d. Presence of suspended particles

Powerful electrolyte particles like NaCl, (NH4)2, SO4 along with moisture
accelerate the electrochemical corrosion.

e. Effect of pH and electrode potential

The corrosion rate with respect to pH and electrode potential of metals is studied
with the help of a Pourbaix diagram.
The Pourbaix diagram for iron (Fig. 3.13.) shows that metallic iron consists of
two regions of corrosion, the passivity region and the immunity region. The Passivity
region indicates low corrosion rate, due to the formation of a protective metal oxide
layer on the metal. The Immunity region indicates no corrosion, since this region has
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an internal cathodic protection. These two regions signify the release of iron into the
solution. In the diagram, 'Z' is the point where pH is 7 and the electrode potential is –
0.4 V. It is present in the corrosion zone.

Pourbaix diagram

Fig. 3.13. Pourbaix diagram

This clearly shows the iron rusts in water under those conditions. In actual practice,
it is observed to the true. The corrosion rate can be changed by creating a shift in the
point 'Z' into immunity or passivity regions. The iron becomes immune when the
potential is changed to about – 1.2 V by applying external current. The rate of
corrosion of iron can also be decreased by moving the point to the passivity region on
applying a positive potential. The diagram clearly indicates that the rate of corrosion
can also be decreased by increasing the pH by adding an alkali.
Thus, the rate of corrosion will be maximum when the corrosive environment is
acidic. i.e. pH is less than 7.

Corrosion Control
By cathodic protection
When a metal is in contact with an electrolyte, there is a high chance of it to
get corroded. Cathodic protection plays an important role to save these metals from
getting corroded. The principles involved in the cathodic protection makes a metal to
behave like a cathode.
The important cathodic protections are
(i) Sacrificial anodic protection.
(ii) Impressed current cathodic protection.
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(i) Sacrificial anodic protection method
A Sacrificial Anode is a metal that is highly active. It prevents less active
material surface that are in the more anodic region in the electrochemical series from
corroding. The sacrificial anode is a metal alloy which placed in the more anodic
region in the electrochemical series which has a more negative electrochemical
potential than the metal that has to be protected. The sacrificial anode gets
consumed. The materials used for sacrificial anodes are zinc or magnesium or
aluminium alloys. Current flows from the sacrificial anode to the protected metal
which becomes more cathodic creating a galvanic cell. The oxidation of the protected
metal gets transferred to the sacrificial anode which gets corroded and thus protects
the metal structure.(Fig. 3.18.)

Fig. 3.18. Sacrificial anodic protection

Applications of sacrificial anodic protection

(a) 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. 3.19.). 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.

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 Fig. 3.19. Sacrificial anodic protection
b. Protection of underground pipelines and cables from soil corrosion (Fig. 3.19.).
c. Insertion of Mg sheets into the domestic water boilers to prevent the formation of
rust (Fig. 3.19.).
d. Calcium metal is introduced to decrease engine corrosion.

(ii)Impressed current cathodic protection method (ICCP)

Since sacrificial anodes cannot deliver enough protection to large structures
impressed current cathodic protection method is used. It is used in larger structures
where electrolyte resistivity is high. It consists of an anode connected to a power
source. Anodes used may be tubular or solid rod shapes or continuous ribbon
shaped. They contain silicon cast iron, platinum, graphite and mixed metal oxide.
They are connected with a niobium coated wire.

Fig.

3.20. Impressed current cathodic protection

For huge pipelines such as those used in oil wells and for water supply anodes are
set in ground beds depending on the field condition including current distribution
requirements. The rectifier is connected to the anode and the output is connected to
the structure to be protected through cathodic protection system. An optimised
power has to be provided to give protection to the target structure. The operating
current output is often checked to make sure there is proper supply. ICCP‘s is
normally used in structures present in shores and complex structures. (Fig. 3.20.)
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Application of impressed current protection
Structures like tanks, pipelines, transmission line towers, underground water pipe
lines, oil pipe lines, ships etc., can be protected by this method.

Table 3.2 Comparison of Galvanic method (Sacrificial anode) and impressed

current Cathodic method

Sl.No. Sacrificial anodic method Impressed current method

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

Metallic Coatings

Electroplating (or) Electro–deposition

Electroplating is the process in which the coating a metal such as Nickel or
Copper or Gold is deposited on the base metal such as iron or steel by passing a
direct current through an electrolytic solution such as corresponding soluble salt of
the coating metal. Electroplating is used to change the properties like abrasion, wear
resistance, corrosion protection, lubricating power and aesthetic qualities of a metal.

Construction
Pure nickel metal is made as anode. The object to be coated acts as cathode.
Both the anode and the cathode are immersed in a solution of Nickel sulphate, Nickel
chloride and Borax mixture. Anode and cathode are connected to an external power
supply. The following conditions are maintained for Nickel plating.
Ni Pellets or pieces in Titanium
Anode
mesh
Electrolyte Nickel sulphate NiSO4.6H2O 240-300 g/l

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 Nickel chloride NiCl2.6H2O 30-90 g/l
Boric acid H3BO3 30-45 g/l
Water
Coumarin, Saccharin, Benzene
Additives
sulphonamide
Operating Temperature: 105-150°F
pH 3.0-4.5
Cathode current density 20-100 mA cm-2
Brighteners p-toluene sulfonamide, benzene
sulphonic acid
Levelers, second class allyl sulfonic acid, formaldehyde
brighteners chloral hydrate

Working
In the anode, oxidation occurs where Ni atoms are converted in to Ni2+ ions
and dissolves in to the solution. The dissolved metal ions in the electrolyte solution
moves towards the cathode. These Ni2+ ions get reduced at the cathode and deposit
as Ni at the object. The rate at which the anode is dissolved is equal to the rate at
which the cathode is plated. The rate of plating also depends on the current flowing
through the circuit.
At anode: Ni → Ni2+ + 2e–

At Cathode: Ni2+ +2e– →Ni

In order to get strong, adherent and smooth deposit certain additives (glue, gelatin,
etc.,) are added to the electrolytic bath.To improve the brightness of deposit,
brightening agents are added in the electrolytic bath.

Application:
1. It used to improve the appearance of exterior auto parts, such as grills and
bumpers.
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2. Nickel electroforming, is commonly used in the aerospace, textile and
communication industries.

Advantages:
1. It used to improve the physical properties such as resistance to wear, heat or
corrosion.
2. It serves the dual purpose of providing a bright, attractive finish as well as
imparting improved corrosion resistance

ALLOYS

Introduction
All engineering disciplines need to know about materials and its properties. In the
making of a new device or component, selection of the right material is very
important.
Another dimension an engineer is
 To select a material for a given use based on considerations of cost and
performance.
 To understand the limits of the materials and accordingly create or design a
new material that will have some desirable properties.
Pure metals possess few important physical and metallic properties, such as melting
point, boiling point, density, specific gravity, high malleability, ductility, and heat and
electrical conductivity. Metallic materials used for engineering purposes are alloys.
Metals are alloyed with some other metal or nonmetal, to improve their properties,
such as strength, hardness, colour, castability and corrosion resistance.

Definition
Homogenous solid solutions of two or more different elements, one of which is
essentially a metal. Metals (solute) can dissolve in another metal (solvent) in molten
state and form alloy (solid solution) on solidification. An alloy is formed
by melting together two or more elements and they crystallize on cooling into
a solid solution or intermetallic compound.

Purpose of making alloys

i. Enhance the hardness of a metal

An alloy is harder than its component elements. Pure metals are mosty soft. The
hardness of a metal can be improved by alloying it with another metal or non metal.
Pure gold is deep yellow in colour and is soft and malleable. The coloured gold alloys
range in gold content from 8 to 22 carats (33.3% - 91.6% gold) and can be obtained
in a range of colour shades. Yellow Gold or ornamental gold (22K) consists of Gold
91.67%, Silver 5%, Copper 2%, Zinc 1.33%. KDM means that the ornament was

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soldered with Cadmium. Hallmark is a purity certification of gold ornaments in
accordance with Indian standard specifications.
Addition of 0.5% arsenic makes lead so hard and used for making bullets.

ii. Lower the melting point

Pure metals have very high melting point. The melting point gets reduced when pure
metals are alloyed with other metals or nonmetals. This makes the metals melt
easily. This property is utilized to make useful alloys called solders. Wood's metal (an
alloy of lead, bismuth, tin and cadmium) melts at 60.50C, which is far below the
melting points of any of the metals present in it.

iii. Enhance tensile strength

Alloy formation increases the tensile strength of the parent metal.
iv. Enhance corrosion resistance:
Alloys are more resistant to corrosion than pure metals. Pure metals are chemically
reactive and can be easily corroded by the surrounding atmospheric gases and
moisture. Alloying a metal increases the inertness of the metal, which, in turn,
increases corrosion resistance.

v. Modify color
The color of pure metal can be modified by alloying it with other metals or nonmetals
containing suitable color pigments.

vi. Provide better castability

One of the most essential requirements of getting good castings is the expansion of
the metal on solidification. Pure molten metals undergo contraction on solidification.
Metals need to be alloyed to obtain good castings because alloys expand.

Functions (or) Effect of Alloying Elements

Addition of small amounts of alloying elements imparts some special properties
like hardness, tensile strength, resistance to corrosion and coefficient of expansion,
on steel. Such products are known as special steels or alloy steels. Some
important alloying elements and their functions are given in Table 6.1.

Table 6.1 Functions of alloying elements

Alloying Element Effect on properties
Carbon (C) Decreases the ductility, formability, weldability
Increases the strength and hardenability.
Manganese (Mn) Increases the strength, shock resistance, toughness,
hardenability, weldebility, hot formability,
Silicone (Si) Increases strength, decreases the weldability, magnetic
losses, oxide formation affinity, no change in ductility.
In addition Si has higher affinity to ‘O’ than carbon
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 therefore used as deoxidizing agent (semi-killed steels).
Chromium (Cr) Increases, strength, hardenability, corrosion resistance,
high temperature strength, forms a very coherent oxide
layer on the surface preventing further oxidation in
stainless steels
Nickel (Ni) Increases the strength, toughness (even at sub zero
temperatures) and hardenability,
Fine grains are produced.
Vanadium (V) and Increases the strength, high temperature strength, wear
Tungsten (W) resistance, since both are strong carbide formers widely
used in HSS tools.
Increases tensile strength and resistance to abrasion
Grain structure is refined.
Increase in magnetic retentivity as well as cutting
hardness.
Molybdenum (Mo) Increases the hardenability, high temperature strength,
decreases the risk for temper embrittlement (~0.5 % Mo).
Since the melting point of molybdenum carbide is very
high, it provides high temperature strength which is very
useful in some HSS (high speed steel) tools.
Zirconium (Zr) Strong carbide formers even better than Cr. Therefore
and Titanium (Ti) commonly used in austenitic stainless steel to free the Cr
and thus further increase the corrosion resistance.
Providing very fine grain size which is the reason to high
strength and ductility of low alloy (HSLA) steel, commonly
used in automotive industry.

Heat treatment of alloys (steel)

Heat treatment is defined as” the process of heating and cooling of solid steel article
under carefully controlled condition”. During heat treatment certain physical
properties are altered without altering its chemical composition.
Objectives (or) purpose of heat treatment
Heat treatment causes
Improvement in magnetic and electrical properties.
Refinement of grain structure.
Removal of the imprisoned trapped gases.
Removal of internal stress.
Improves fatigue and corrosion resistance
Used in making chemical equipment’s & automobile parts.

1. Annealing
Annealing means softening. This is done by heating the metal to high temperature
followed by slow cooling in a furnace.
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Purpose of annealing
i. It increases the machinability.
ii. It also removes the imprisoned gases.
Types of annealing
Annealing can be done in two types
Low temperature annealing (or) process annealing
High temperature annealing (or) full annealing
(i)Low temperature annealing (or) process annealing
It involves in heating steel to a temperature below the lower critical point followed by
slow cooling.
Purpose
1. It improves machinability by reliving the internal stress or internal strain.
2. It increases ductility and shock resistance.
3. It reduce hardness.
(ii) High temperature annealing (or) full annealing
It involves in heating to a temperature about 30 to 50⁰C above the higher critical
temperature and holding it at that temperature for sufficient time to allow the
internal changes to take place and then cooled room temperature.
The approximate annealing temperature of various grades of carbon steel are
1. Mild steel=840-870⁰C
2. Medium carbon steel=780-840⁰C
3. High carbon steel=760-780⁰C
Purpose
1. It increases the ductility and machinability.
2. It makes the steel softer, together with an appreciable increase in its toughness.

2. Hardening (or) quenching

It is the process of heating steel beyond the critical temperature and then suddenly
cooling it either in oil or brine water or some other fluid.
The faster the rate of cooling harder will be the steel produced.
Medium and high carbon steel can be hardened but low carbon steel cannot be
hardened.
Purpose
1. It increases its resistance to wear ability, to cut other metal and strength .
2. It increases abrasion resistance.
3. Used for making cutting tools.

3. Tempering
It is the process of heating the already hardened steel to a temperature lower than
its own hardening temperature & then cooling it slowly.
The temperature to which hardened steel is reheated controls the development of
the final properties.
Thus,
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(a)For retaining strength & hardness, reheating temperature should not exceed
400⁰C.
(b) For developing better ductility & toughness, reheating temperature should be
within 400-600⁰C.
Purpose
1. It removes stress & strains that might have developed during quenching.
2. Increased toughness & ductility.
3. Used for cutting tools like blade, cutters etc.

4. Normalising
It is the purpose of heating steel to a definite temperature (above its higher critical
temperature) & allowing it to cool gradually in air.
Purpose
1. Recovers homogeneity.
2. Refines grains.
3. Removes internal stresses.
4. Increases toughness.
5. Used in engineering works.
NOTE: The difference between normalised & annealed steel are
1. A normalised steel will not be as soft as annealed steel.
2. Also normalizing takes much lesser time than annealing.

5. Carburizing
The mild steel article is taken in a cast iron box within containing small pieces of
charcoal (carbon material).
It is heated to about 900 to 950⁰C & allow it for sufficient time, so that the carbon is
absorbed to required depth .
The article is then allowed to cool slowly within the box itself.
The outer skin of the article is converted into high carbon steel containing about 0.8
to 1.2% carbon.
Purpose
To produce hard surface on steel article.

6. Nitriding
Nitriding is the process of heating the metal alloy in presence of ammonia to about
550⁰C.
The nitrogen (obtained by the dissociation of ammonia) combines with the surface of
the alloy to form hard nitride.
Purpose
To get super-hard surface.

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Classification Of Alloys
Alloys are broadly of two types namely ferrous and non-ferrous alloys. This
classification is primarily based on the quantity of materials used all over the world.
Ferrous materials are those in which iron (Fe) is the main constituent. All other
alloys are categorized as non-ferrous alloys.

Alloys

Ferrous Alloy Non- ferrous Alloy

Steel Cast Iron Solder

Carbon Grey Brass

Low Alloy White Bronze

High
Malleable
Alloy

Nodular

Ferrous Alloys or Alloy Steels

Ferrous alloys which contain elements like Al, B, Cr, Co, Mn in sufficient quantities in
addition to C & Fe. In ferrous alloys the main alloying element is carbon (C).
Depending on the amount of carbon present, these alloys will have different
properties. Thus the ferrous alloys with less than 2.14% C are termed as steels, and
the ferrous alloys with higher than 2.14% C are termed as cast irons.

Properties
1. It possesses high yield point & high strength.
2. It possesses sufficient formability, ductility & weldability.
3. They are Corrosion & abrasion resistant.
4. Less distortion & cracking.
5. It possesses high temperature strength.

Important Ferrous Alloys

Stainless Steels (or) Corrosion Resistant Steels
Steels are made highly corrosion resistant by addition of special alloying elements,
especially a minimum of 12% Cr along with Ni and Mo. Chromium is effective if its

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content is 16% or more. The carbon content in stainless steel ranges from 0.3 to
1.5%. Protection against corrosion is mainly due to the formation of dense, non –
porous, tough film of chromium oxide at the surface of metal.

Properties
1. Resist corrosion by atmospheric gases & also by other chemicals.
2. Protection against corrosion is due to the formation of dense, non- porous, tough
film of chromium oxide at the metal surface. If the film cracks, it gets automatically
healed up by atmospheric oxygen.

Types of Stainless Steel

There are two main types of stainless steels.
1. Heat treatable stainless steel, 2. Non- heat treatable stainless steel
1. Heat Treatable Stainless Steel can be hardened and strengthened by heat
treatment process.
Composition: Carbon-1.2%, Chromium-less than 12-16%
Properties
They are magnetic, tough & can be worked in cold condition.
Uses
1. They can be used up to 800⁰C.
2. They are very good resistant towards weather & water.
3. Used in making surgical instruments, scissors, blades, etc.
2. Non - Heat Treatable Stainless Steel are hardened and strengthened by cold
work because they are not heat treatable.
Properties
Possess less strength at high temperature.
Resistant to corrosion.

Types of Non Heat Treatable

Stainless Steel
(1) Magnetic Type (2) Non Magnetic Type
Composition: Chromium-12-22% , Composition: Chromium-18-26%,
Carbon-0.35% Nickel-8-21%, Carbon-0.15%
Total % of Cr & Ni is more than 23%.
Properties: 18/8 Stainless Steel
1. It can be forged, rolled & machined Composition: Chromium-18%, Nickel-
by the use of specially designed tools. 8%
2. Resist corrosion. Properties
1. Resistance to corrosion.
2. Corrosion resistance is increased by
adding little quantity of molybdenum.
Uses

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 Used in making household utensils,
sinks, dental & surgical instruments.

Non – Ferrous Alloys

These alloys do not contain iron as one of the main constituent. The main
constituent of non-ferrous alloys are copper, aluminium, lead, zinc, tin, etc.
Generally, the melting points of non-ferrous alloys are lower than those of ferrous
alloys. Non ferrous alloys are expensive compared to steels.

Properties of Non-ferrous alloys

Non-ferrous materials have specific advantages over ferrous materials. They can be
fabricated with ease, high relatively low density, and high electrical and thermal
conductivities. However different materials have distinct characteristics, and are
used for specific purposes. This section introduces some typical non-ferrous metals
and their alloys of commercial importance.
They are widely used because of their
 Softness and good formability
 Resistance to corrosion -
 Attractive colors.
 Good electrical and magnetic properties
 Low density and co-efficient of friction.

Important Non-Ferrous Alloys

Brass
Brasses are copper alloys in which the principal alloying element is zinc. Their
properties depend mainly upon the percentage of zinc present but can be modified by
the addition of new elements to further improve properties such as strength,
machinability or resistance to corrosion.
Commercially important Brasses their properties and uses
Some important brasses and their composition, properties and uses are given in the
following table
Type of Brass Composition Properties and Applications
(ii) Dutch - metal Cu = 80% It is golden in colour.
(or) Low brass Zn = 20% It is suitable for all drawing and
forming operations.
It is used in imitation jewellery, battery
caps, flexible hoses, tubes etc.,
German silver Cu = 25 – 50% It is ductile malleable and looks like silver
Zn = 10 – 35% It possesses good strength and
Sn = 5 – 35% corrosion resistance to salt water.
Utensils, bolts, screws, ornaments,
coinage decorative articles.

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 QUESTION BANK (2 MARKS)
PART A
1. What is corrosion? Mention its types.
The gradual deterioration or degradation of a material due to a reaction with its
environment is called as corrosion. The types are:
A) Dry or chemical corrosion
 Oxidation corrosion
 Corrosion by hydrogen
 Liquid-metal corrosion
B) Wet or electrochemical corrosion
 Galvanic corrosion
 Differential aeration.

2. What is Pilling-Bedworth ratio? State its importance.

The Pilling-Bedworth ratio or P-B ratio is the ratio of the volume of the metal
oxide formed to the volume of metal consumed.
P-B ratio = Volume of metal oxide formed
Volume of metal consumed
Importance of P-B ratio:
Through this ratio we can predict whether the metal is likely to form a
protective oxide layer.

3. Distinguish between chemical and electrochemical corrosion.

SI.NO CHEMICAL CORROSION ELECTROCHEMICAL CORROSION

It occurs in the presence of water or
1 It occurs only in dry condition
electrolyte.
It is due to the setup of a large
It is due to the direct chemical attack
2 number of cathodic and anodic
of metal on the environment
areas.
Even a homogeneous metal surface It requires a heterogeneous surface
3
gets corroded or bimetallic contact.
Corrosion products accumulate Corrosion occurs at the anode, while
4
where the corrosion occurs. products formed elsewhere.
5 It is self-controlled. It is a continuous process.
Follows adsorption mechanism. Follows electrochemical reaction.
6 Eg: formation of mild scale on iron Eg: rusting of iron in moist
surface. atmosphere.
4. Define galvanic corrosion.

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The corrosion that occurs when two different metallic materials are connected with
each other in the presence of moisture or electrolyte. The material which is more
anodic will corrode.
Example: Steel screw in a brass marine hardware corrodes.

5. What is differential aeration corrosion?

Corrosion of metals due to the uneven supply of air on the metal surface is known as
differential aeration corrosion.
At anode: M M2+ + 2e-
At cathode: 1/2O2 + H2O +2e- 2OH-
Example : Pipeline corrosion and Pitting corrosion

6. Steel screw in brass hardware corrodes. Why?

This is due to the galvanic corrosion. Iron which has higher position in
electrochemical series becomes an anode and gets corroded, while brass which is
lower in electrochemical series act as cathode and gets not attacked.

7. What is pitting corrosion?

Pitting corrosion is a type of differential aeration corrosion. It occurs in an area where
there is a formation of a hole and the area around the metal is unattacked.
At anode: Fe Fe2+ +2e-
At cathode: 1/2 O2 + H2O + 2e- 2OH-
Net reaction: Fe2++ 2OH- Fe(OH)2 Fe(OH)3
Example: Metal area covered by water droplet.
8. What is pipeline corrosion?
Differential aeration corrosion may also occur in different parts of pipeline. Buried
pipelines or cables passing through the soil, from one type of soil to another say,
from clay that is less aerated to sand that is more aerated may get corroded due to
differential aeration.

9. Zinc is more readily corroded when coupled with Cu than with Pb. why?
This is due to the galvanic corrosion. When the two different metals like Cu and Zn
are in direct contact with each other then Cu (E0 = +0.34 V) acts a cathode and Zn
(E0 = - 0.76 V) acts as anode.
At anode: Zn Zn2+ + 2e-
Zn2++ 2OH- Zn(OH)2
At cathode: Cu + 2e
2+ - Cu
Thus due to the above reaction, Zn gets corroded.

10. Small anodic area results in intense corrosion. Why?

The rate of corrosion is rapid and intense if anodic area is smaller and the cathodic
area is bigger because the demand for electron is more.

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11. Defne electroplating.
It is a process in which the coating metals such as copper or gold on the base metals
such as iron or steel by passing a direct current through an electrolytic solution
containing the soluble salt of the coating metal such as CuSO4 or AuCl3.
Example: Electroplating of copper over iron.

12. Bolt and nut of same metal are preferred in practice.

To avoid galvanic corrosion, it is made up of the same metal so it has no anodic and
cathodic part.

PART B
1. Describe the mechanism of electrochemical corrosion by hydrogen evolution and
oxygen absorption.
2. What is chemical corrosion? Explain the mechanism of oxidation corrosion.
3. How corrosion is prevented in ship hulls and transmission line towers. Explain.
4. Explain galvanic corrosion with suitable examples.
5. State and explain pilling–bedworth rule.
6. Explain the electrochemical theory of corrosion with suitable example.
7. Define corrosion and explain the various factors influencing corrosion of a
metal.
8. What is cathodic protection? Explain the sacrificial anode and impressed
9. Explain differential aeration corrosion with an example.
10. Describe the important parameters involved in the electroplating.
11. What are the main objectives of electroplating? Give account of the method used
in electroplating of Nickel.
12. What is the main purpose of alloying steel?
13. Write note on heat treatment of steel.
14. What are the non ferrous alloys? Give their properties.

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