Chapter II

CORROSION
and its CONTROL
CORROSION AND ITS
CONTROL

DEFINITION
Corrosion is defined as the gradual
destruction or deterioration of
metals or alloys by the chemical or
electrochemical reaction with its
environment.
 CONSEQUENCES OF CORROSION

Due to formation of corrosion product over the

machinery, the efficiency of the machine gets lost.

The products gets contaminated due to corrosion.

The corroded equipment must be replaced frequently.

Plant gets failure due to corrosion.

Corrosion releases toxic products, health hazard, etc.

 CLASSIFICATION OF CORROSION
Based on the environment, corrosion is classified in to
1. Dry or Chemical corrosion
2. 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, inorganic liquids
etc.

There are three main types of dry corrosion;

1. Oxidation corrosion (or) corrosion by oxygen

2. Corrosion by hydrogen.
3. Liquid – metal corrosion.
 OXIDATION CORROSION

 Oxidation corrosion is brought about by the direct

attack of oxygen at low or high temperatures on
metal surface in the absence of moisture.
 Alkali metals like (Li, Na, K, etc) and alkaline-earth
metals (Mg, Ca, Sr, etc) are rapidly oxidised at low
tempt.
 At high temperature, almost all metals (expect Ag,
Au and Pt) are oxidized.
 MECHANISM OF DRY CORROSION

Oxidation occurs first at the surface of the metal

resulting in the formation of metal ions (M2+), which
occurs at the metal/oxide interface.
M → M2+ +2e-

6
Oxygen changes to ionic form (O2-) due to the
transfer of electron from metal, which
occurs at the oxide film / environment
interface.
½ O2 + 2e- → O2-

Oxide ions reacts with the metal ion to form

the metal- oxide film.

M + ½ O2 → M2+ +O2- ≡ MO (Metal-oxide film)

 NATURE OF OXIDE FILM

The nature of oxide film formed on the metal surface plays in

important role in oxidation corrosion.

(i) STABLE OXIDE LAYER

A stable oxide layer behaves as a protective

coating and no further corrosion can develop.
Example: oxides of Al, Sn, Pb, Cu, etc., are stable oxide layers.

(ii) UNSTABLE OXIDE LAYER

Unstable oxide layer is mainly produced on the surface of

noble metals, which decomposes back in to the metal and
oxygen.
Metal oxide → Metal +Oxygen

Example: Oxides of Pt, Ag, etc., are unstable oxide layers.

(iii) VOLATILE OXIDE LAYER
The oxide layer volatilizes as soon as it is
formed, leaving the metal surface for further
corrosion.

Example: Molybdenum oxide is volatile.

(iv) POROUS OXIDE LAYER

Metal oxides having pores and cracks allow
penetration of oxygen to the underlying
metal, resulting in the complete conversion
of metal into its oxide.
 PILLING –BEDWORTH RATIO

• The ratio of the volume of the oxide formed to

the volume of the metal consumed is called
“pilling-bedworth ratio”.

R = Md/nmD

Where M - mass of metal oxide

m - atomic weight
d - density of the metal
D - density of the scale
n- number of metal atoms in a formula of the scale
(PILLING-BEDWORTH RULE)

According to Pilling–Bedworth rule,

1. If the volume of the oxide layer formed is less than the

volume of the metal, the oxide layer is porous and non-
protective.
Example: Oxides of alkali and alkaline earth metals.

2. If the volume of the oxide layer formed is greater than the

volume of the metal, the oxide layer is subjected to cracking
and spalling resulting in poor oxidation resistance and
protection.
Example: Oxides of heavy metals such as Sb,V, W, etc.

3. If the volume of oxide layer is equal to the volume of the

metal then there will be protective oxide film formation.
Example: Oxides of Al, Pb, Ni, etc.
11
 CORROSION BY OTHER GASES

 Gases like SO2, CO2, Cl2, H2S etc – induce corrosion

action on metals
 Corrosion effect depends on the chemical affinity
between the metal and the gas.
 The degree of attack by gases depends on the formation
of protective or non-protective films on the metal
surface.
(1) If the film is non-porous or protective, the intensity of
attack decreases. Eg. AgCl film – attack of Cl2 on Ag
(2) If the film is porous or non-portective, the surface of the
whole metal is gradually destroyed.
Eg. Dry Cl2 gas attack on Sn – formation of volatile SnCl4
– fresh surface is exposed for further attack 12
 CORROSION BY HYDROGEN

(a) HYDROGEN EMBRITTLEMENT:

Contact of metal with H2S results in the generation of
atomic hydrogen
E.g. Fe + H2S → FeS + 2H
H + H → H2 ↑

Corrosion caused by the exposure of metal to hydrogen

environment.
Hydrogen in atomic state diffuses into the metal matrix
and collects in the voids present in the metal.
The hydrogen atoms combine to form H2 gas.
A very high pressure is developed, which results in cracks
and blisters on metal. This process is called hydrogen
embrittlement.
(b) DECARBURISATION
At higher temperature atomic hydrogen is
formed by the thermal dissociation of molecular
hydrogen.
H2 → 2H
When steel is exposed to this environment, the
atomic hydrogen readily combines with carbon
of steel and produces methane gas.
C + 4H → CH4↑
Collection of these gases in the voids develop
very high pressure, which causes cracking. Thus
the process of decreases in carbon content in
steel is termed as “Decarburisation” of steel.
 LIQUID - METAL CORROSION
This is due to the chemical action of
flowing liquid metal at high temperature.
The corrosion reaction involves either,

(i) Dissolution of a solid metal by a liquid

metal (or)

(ii) Liquid metal may penetrate in to the

solid metal.
 WET (or) ELECTRO-CHEMICAL
CORROSION

Wet corrosion occurs under the foll. conditions,

 When two dissimilar metals are in contact with each

other in the presence of an aqueous solution or
moisture.

 When two dissimilar parts of the same metal are in

contact with an aqueous solution of an electrolyte.
 MECHANISM OF WET CORROSION
According to electrochemical theory of corrosion,
the wet corrosion involves two steps.
a) Oxidation or metal dissolution
b) Reduction

Metal dissolution occurs always at anode leading to

the formation of metal ions and electrons
M → Mn+ + ne-

At cathode, electron consumption resulting in either

evolution of hydrogen or absorption of oxygen
depending on the nature of corrosion environment.
17
(a) Acidic environment

If the corrosive environment is acidic, hydrogen evolution

occurs at cathodic part.

2H+ + 2e- → H2↑

(b) Alkaline or Neutral environment

If the corrosive environment is slightly alkaline (or) neutral,

hydroxide ion forms at cathodic part.

½ O2 + 2e- +H2O → 2OH-

Thus the metal ions (from anodic part) and non-metallic ions
(from cathodic part ) diffuse towards each other through
conduction medium and form a corrosion product between
anode and cathode.
 a) Hydrogen evolution type corrosion
 Metals have negative reduction potential
i.e., below hydrogen reduction potential
value in the electrochemical series get
dissolved in acidic solution with
simultaneous liberation of “hydrogen gas”.
 Example: Iron metal in contact with non-
oxidizing acid like HCl results in H2
evolution
 At anode: Iron (Fe) undergoes dissolution to
Fe2+ with the liberation of electrons.
 At cathode: The liberated electrons follow
from anode to cathode, where H+ ions get
reduced to H2.
19
 b) Absorption of oxygen or formation of hydroxide
ion type corrosion
 Fe surface usually contains a coating of Iron oxide and if
this oxide layer develops, cracking happens.
 As a result anodic areas are created on the surface and
remaining area acts as cathode.
 Example: Iron metal in contact with a neutral solution of
electrolyte in the presence of O 2, OH- ions are formed.
 At anode: Iron (Fe) undergoes dissolution to Fe 2+ with the
liberation of electrons.
 At cathode: The liberated electrons follow from anode to
cathode, where dissolved O2 is consumed to form OH- ions.
1/2O2 + H2O + 2e- 2OH-
Fe2+ + 2OH- Fe(OH) 2
Fe(OH)2 + 2H2O + O2 4Fe(OH)3 (rust)

20
 Chemical Corrosion Electrochemical Corrosion
It occurs only in dry condition It occurs in the presence of
moisture or electrolyte
It is due to the direct chemical It is due to the set up of a
attack of the metal by the large number of cathodic and
environment anodic areas
Even a homogeneous metal Hetergeneous surface or
surface gets corroded bimetallic contact is required
for corrosion
Corrosion products Corrosion occurs at the anode,
accumulate in the same place, while products formed
where corrosion occurs. elsewhere
Chemical corrosion is self- It is continuous process
controlled
It follows adsorption It follows electrochemical
mechanism reaction
Eg. Formation of mild scale on Eg. Rusting of iron in moist
iron surface atmosphere 21
TYPES OF ELECTROCHEMICAL CORROSION

GALVANIC CORROSION

When two different metals are in contact with each

other in the presence of an aqueous solution or moisture,
galvanic corrosion occurs. Here, the more active metal
(with more negative electrode potential) acts as anode and
the less active metal (with less negative potential) acts as
cathode.

Example for galvanic corrosion

Steel screw in a brass marine hardware corrodes. This is
due to galvanic corrosion. Iron (higher position in
electrochemical series) because anodic and is attacked and
corroded, while brass (lower in electrochemical series) acts
as cathodic and is not attacked.
Bolt and nut made of the same metal is preferred.
Why?
It is preferred in practice, because galvanic
corrosion is avoided due to homogeneous metals (no
anodic and cathodic part).

Prevention:
 Avoid unfavorable area effect
 Selection of metals & alloys
 Insulating dissimilar metals
 Using inhibitors
 Applying cathodic protection
 DIFFERENTIAL AERATION CORROSION

This type of corrosion occurs when a metal is

exposed to varying concentration of oxygen or any
electrolyte on the surface of the base metal.

Example

• Metals partially immersed in water (or) conducting

solution (called water line corrosion).

• If a metal is partially immersed in a conducting

solution the metal part above the solution is more
aerated and hence become cathodic.

• On the other hand, the metal part inside the

solution is less aerated and thus, become anodic
and suffers corrosion.
At anode (less aerated) corrosion occurs
M → M2+ +2e-
At cathode (more aerated part) OH- ions are produced
½ O2 +H2O + 2e- → 2 OH- 25
Examples for differential aeration
corrosion

 Pitting or localized corrosion

 Crevice corrosion
 Soil corrosion.
 Corrosion on wire fence.

26
(a) Pitting Corrosion

This is a localised attack, resulting in the formation

of a hole around which the metal is relatively
unattacked.

Example
Metal area covered by a drop of water, sand, dust,
scale etc.,

• Consider a drop of water or aqueous NaCl resting

on a metal surface.

• The area covered by the drop of H2O acts as an

anode due to less O2 conc., and suffers corrosion.

• The uncovered area (freely exposed to air) acts 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. A small
hole or pit is formed on the surface of the metal.

At anode
Iron is oxidized to Fe2+ ions (Fe → Fe2+ +2e-)

At cathode
Oxygen is converted to OH- ions. (1/2O2 +H2O +2e- → 2OH-)

Net reaction is
Fe2+ +2OH- → Fe(OH)2 →Fe(OH)3
This type of corrosion is called pitting. 28
 (b) Crevice corrosion

• If a crevice between different metallic objects or

between metal and non-metallic material is in
contact with liquids, the crevice becomes the
anodic region and suffers corrosion.
• This is due to less oxygen with crevice area.
• The exposed areas act as the cathode.
 (c) PIPELINE CORROSION
• Differential aeration corrosion may also
occur in different parts of pipeline.
• Buried pipelines or cables passing from one
type of soil to another, example from clay
(less aerated) to sand (more aerated) may get
corroded due to differential aeration.
 (d) CORROSION ON WIRE-FENCE
• A wire fence in which the areas where the wires cross are
less aerated than the rest of the fence and hence corrosion
occurs at the wire crossings, which are anodic.

Other examples for differential aeration corrosion

(i) Corrosion occurring under metal washers, where oxygen
cannot diffuse easily.

(ii) Lead pipeline passing through clay to cinders undergo

corrosion. Since the pipeline under cinders is more aerated,
it gets corroded easily.
 FACTORS INFLUENCING CORROSION
The rate and extent of corrosion depends
mainly on
i. Nature of the metal
ii. Nature of the environment

Nature of the metal

A) Position in EMF series

 The extent of corrosion depends upon the

position of the metal in the EMF series.
 Greater the oxidation potential, greater is the
rate of corrosion.
 When two metals are in electrical contact, the
metal higher (-) ve electrode potential in the EMF
series becomes anodic and suffers corrosion.
 Further, the rate and severity of corrosion depends
upon the difference in their positions in the EMF
series.
 Greater the difference, faster is the corrosion of
anodic metal.

(b) Relative areas of the anode & cathode

 The rate of corrosion is more when area of the
cathode is larger.
 When cathodic area is larger, the demand for
electrons will be more and this results in an
increased rate of dissolution of metals at anodic
regions.
(c) Purity of the metal
 The 100% pure metal will not undergo any type
of corrosion.
 But, the presence of impurities in a metal
create heterogeneity and thus galvanic cells are
sets up with distinct anodic and cathodic area
in the metal.
 Higher the percentage of impurity, faster is the
rate of corrosion of the anodic metal.

(d) Physical state of the metal

 Metal components subjected to unevenly
distributed stresses are easily corroded.
 Even in a pure metal, the areas under stress
tend to be anodic and suffer corrosion.
(f) Nature of the Corrosion Product

 If the corrosion product is soluble in the

corroding medium, the corrosion of the
metal will proceed faster.

 On the other hand, if the corrosion

product is insoluble, then the protective
film formed will tend to suppress corrosion.

35
 (G) Nature of the oxide film
 Metals such as Mg, Ca, Ba, etc., form oxides
whose volume is less than the volume of the
metal.
 Hence, the oxide film formed will be
porous, through which oxygen can diffuse
and bring about further corrosion.
 On the other hand metals like Al, Cr, Ni
etc. form oxides whose volume is greater
and the non-porous oxide film so formed
will protect the metal from further
corrosion.
36
 NATURE OF THE ENVIRONMENT
(A) Temperature
 The rate of chemical reaction and the rate
of diffusion of ions increases with rise in
temperature
 Hence, corrosion increases with
temperature.
 A passive metal may become active at a
higher temperature.

37
(B) Humidity
The rate of corrosion will be more, when
the humidity in the environment is high.
The moisture acts as a solvent for the
oxygen in the air to produce the
electrolyte, which is essential for setting
up a corrosion cell.
Rusting of iron increases when the
relative humidity of air reaches from
60 to 80 percent.

38
(C) Effect of pH

The rate of corrosion is maximum when

the corrosive environment is acidic.
In general, acidic environment is more
corrosive than alkaline or neutral medium.
Corrosion rate can be reduced by
increasing the pH of the medium.
But metals such as Al, Zn dissolves in
alkaline medium.

39
 (D) NATURE OF THE ELECTROLYTE

 If the electrolyte consists of silicate ions,

they form insoluble silicates and prevent
further corrosion.

 On the other hand if chloride ions present,

they destroy the protective film and the
surface is exposed for further corrosion.

 If the conductance of electrolyte is more,

the corrosion current is easily conducted
and hence the rate of corrosion is
increased.
40
(E) Conductance of the corroding medium
The corrosion current depends upon the
internal resistance of the short circuited
cells, which in turn depends on the
conductance of the electrolytic medium.
If the conductance of the soil is more, the
corrosion of underground structure will
also be more.
Conductance in clayey, soils and
mineralized soils is more.

41
 CORROSION CONTROL
The rate of corrosion can be controlled by either
modifying the metal or the environment.

1. Proper Designing
A major factor in the corrosion failure of a component
is a faulty geometrical design.
Some important design principles are:
1) Avoid crevices
2) Avoid residual moisture
3) Avoid galvanic corrosion
Galvanic corrosion can be prevented by the following
methods,
a) Use an electrical insulators
b) Introduce an easily exchangeable corroding places
4) Avoid protruding parts.
2. Cathodic Protection
• The principle involved in cathodic
protection is to force the metal to be
protected to behave like a cathode.
• Since, there will not be any anodic area on
the metal, corrosion does not occur.

There are two types of cathodic protection.

• Sacrificial anodic protection method
• Impressed current cathodic protection
method.
SACRIFICIAL ANODIC PROTECTION METHOD

• In this method, the metallic structure to be

protected is made cathode by connecting it with
more active metal (anodic metal).
• So that all the corrosion will concentrate only
on the active metal.
• The artificially made anode thus gradually gets
corroded protecting the original metallic
structure.
• Hence this process is otherwise known as
sacrificial anodic protection.
Examples of sacrificial anode
• This method is used for the protection of
ships and boats.
• Sheets of zinc and magnesium are hung
around the hull of the ship.
• Zinc and magnesium being anodic to iron
get corroded.
• Since they are sacrificed in the process
of saving iron (anode), they are called
sacrificial anodes.
Applications of Sacrificial Anode
• Protection of underground pipelines and
cables from soil corrosion.
• Magnesium rods are inserted in to
domestic water boilers or tanks to prevent
the formation of rusty water.
• Calcium metal slag's are employed to
minimize engine corrosion.
 IMPRESSED CURRENT CATHODIC PROTECTION

In this method, an impressed current is

applied in the opposite direction to nullify
the corrosion current and convert the
corroding metal from anode to cathode.
This can be done by connecting negative
terminal of the battery to the metallic
structure to be protected.
Positive terminal of battery is connected to
an inert anode. inert anode used for this
purpose is graphite or platinised titanium.
The anode is surrounded by ‘backfill’
(containing mixture of gypsum, coke,
breeze, sodium sulphate) to improve the
electrical contact between the anode and
the surrounding soil.

APPLICATION OF IMPRESSED CURRENT

PROTECTION
This type of cathodic protection is
applied to open water-box coolers, water
tanks, buried oil and water pipes,
condensers, marine piers, transmission
line towers, etc.,
 Comparison of sacrificial anode and
impressed current cathodic method

Sacrificial anodic Impressed current

method method
No external power External power
supply is necessary. supply must be
This method present.
requires periodical Here anodes are
replacement of stable and do not
sacrificial anode. disintegrate.
Investment is low. Investment is more.
Soil corrosion Soil corrosion
effects are not effects are taken
taken in to in to account.
account.
This is most This method is
economical well suited for
method especially large structures
when short-term and long term
protection is operations.
required.
 Control of corrosion by modifying the
environment

DEAREATION
The presence of increased amount of
oxygen is harmful and increase the
corrosion rate.
Deareation involves removal of dissolved
oxygen by increase of temperature with
mechanical agitation.
It also removes dissolved CO2 of water.
 DEHUMIDIFICATION
In this method, moisture from the air is
removed by lowering the relative humidity of
the surrounding air.
This is done by adding silica gel (or) alumina,
which adsorbs moisture preferentially on its
surface.

ALKALINE NEUTRALISATION
The acidic character of the corrosive
environment (due to presence of H2S, HCl, CO2,
SO2, etc) can be neutralized by spraying alkaline
neutralisers (like NH3, NaOH, lime etc).
 CORROSION INHIBITORS

DEFINITION
A corrosion inhibitors is ‘a substance which when
added to in small quantities to the aqueous
corrosive environment effectively decreases the
rate of corrosion of the metal’.

Inhibitors are classified in to three types,

 ANODIC
 CATHODIC
 VAPOUR PHASE
 ANODIC INHIBITORS

 Chromates, phosphates, tungstates of

transition elements, inhibit the anodic
corrosion reaction by forming sparingly
soluble compound with a newly produced
metal ion.
 They are absorbed on the metal surface
forming a protective film or barrier there-
by reducing corrosion rate.
 This kind of corrosion rate is not fully
reliable since certain areas left uncovered
by the film can produce severe corrosion.
 CATHODIC INHIBITORS

In acidic solution, the main cathodic

reaction is evolution of hydrogen.
2H+(aq) +2e- → H2 (g)
• In an acidic solution, the corrosion can
be controlled by slowing down the
diffusion of H+ ions through the cathode.
• This can be done by adding organic
inhibitors like amines, pyridine, azoles,
etc.
They absorb over the cathodic metal
surface and act as a protective layer.
In a neutral solution, the cathodic reaction
is,
H2O + ½ O2 + 2e- → 2OH-(aq)

The formation of OH- ions is only due to the

presence of oxygen.
By eliminating the oxygen from the medium,
the corrosion rate can be reduced.
O2 can be removed by adding some reducing
agents like Na2SO3 or by deaeration.
Salts of Zn, Mg, Ni are employed as they
form insoluble metallic hydroxide which
forms impermeable self barriers.
 VAPOUR PHASE INHIBITORS
Vapour phase inhibitors are organic inhibitors
which readily sublime and form a protective
layer on the metal surface.

Example : Dicyclohexyl ammonium nitrite,

Benzotriazole.

Vapour phase inhibitors are used in the

protection of machineries, sophisticated
equipments, etc. which are sent by ships.

The condensed inhibitor can be easily wiped

off from the metal surface.
 PROTECTIVE COATING

INTRODUCTION
 Protective coatings are used to protect
the metals from corrosion.
 It acts as a physical barrier between the
coated metal surface and the
environment.
 They impart some special properties such
as hardness, electrical properties and
thermal insulating properties to the
protected surface.
 Protective
coatings

Inorganic coating Organic coating

• Metallic coating 1. Paints
• Chemical 2. Varnishes
Conversion 3. Enamels
4. Ceramic
 Sample Preparation
• Mechanical cleaning – To remove loose scale
and rust, using hammer, wire-brushing, grinding
and polishing.
• Sandblasting – To clean large surface areas in
order to produce enough roughness for good
adherence of protective coating, using sand
with air stream at 25-100 atm.
• Solvent Cleaning – To remove oil, grease, rust
using organic solvents like alcohol, xylene,
toluene, hydrocarbons followed by cleaning hot
water or steam.
60
 Sample Preparation (contd..)
• Alkali Cleaning – To remove old paints that are
soluble in alkaline medium using chemicals like
NaOH, Na3PO4 etc. After cleaning, the metal is
washed with 1% chromic acid solution.

• Acid pickling and etching – Base metal is dipped

inside acid solution at a higher tempt for a long
duration. Acids used are HCl, H2SO4, H3PO4, HNO3,
under dilute conditions.

61
 Metallic coatings
• Anodic coating – Galvanization:
It is produced by anodic coating metals (Zn, Al,
Cd) on the surface of base metal (Fe) based on
the relative negative electrode potential.

• Cathodic coating:
It is produced by cathodic coating metals (Sn,
Cr, Ni) on Fe surface based on the relative
positive electrode potential of coat metal.
62
 Methods of application of
metallic coating
• Hot dipping
• Metal cladding
• Electroplating – Cu, Cr, Ni, Au, Ag
• Cementation
• Vacuum metalizing
• Metal spraying

63
 Hot Dipping
• It is one of the common method of applying
metallic coating on the surface of base metals.
• Hot dipping is a process of coating the base metal
by immersing it in the molten coat metal.
• Examples: Galvanizing and Tinning

64
Galvanizing: Fe or steel is coated with a thin coat
of Zn by immersing in molten Zn to prevent
rusting.
• Fe or steel base metal is cleaned by acid pickling
using dil. H2SO4 (60-90 0C) for 15-20 min.
• Base metal dipped in molten Zn (430 0C) and
then passed through rollers to correct the
thickness of the film.
• NH4Cl flux used to protect the surface of molten
Zn from oxide formation.
• Annealed at 250 0C and cooled slowly
• Coating of Iron pipes, screws, bolts, wires, etc.
• Poisonous for utensils that store food stuffs
65
Tinning: In this process tin is coated over mild
steel sheets immersed in molten tin (Sn).
• The sheet is subject to acid pickling and passed
through a bath of molten tin covered with a flux
of ZnCl2.
• After coating, the sheet is passed through palm
oil to protect from oxidation
• Finally the sheet is passed to roller to get
uniform thickness.
• It is used for the coating of steel, Cu and brass
sheets that store food stuffs.

66
 Metal Cladding
• It is the process of sandwitching the base metal
between two thin layers of coating metal by
hot-rolling the composite to produce a firm
bonding.
• The coat metals are usually metals of least
reactivity (Cu, Ni, Ag, Pt, Ti)
• The cladding layer should be very thin and its
thickness is only 5% of the total composite
metal.
• Duraluminium sandwiched between Al sheets
and hot rolled to produce Alkad composite
which is free from stress corrosion 67
 ELECTROPLATING
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.

Electroplating is probably the most important and

most frequently applied industrial method of
producing metallic coatings. The metal film
produced is quite uniform with little or no pinholes
per unit area.

When the thickness of the deposit increases, the

number of pinholes decreases. 68
• The base metal to be plated is made
cathode of an electrolyte cell, whereas the
anode is either made of the coating metal
itself or an inert material of good electrical
conductivity.

THEORY
If the anode is made of coating metal itself
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. 69
Objectives of electroplating:

(i) To increase the resistance to corrosion and chemical

attack of the plated metal.
(ii) To obtain a polished surface
(iii) To improve hardness and wear resistance

Example: Electroplating of Cu, Au, Ag, Cr, Ni, Sn etc.

Uses of electroplating:

(i) It is often used in electronic industries for making printed circuit

boards, edge connectors, semiconductor lead-out connection
(ii) It is also used in the manufacture of jewelery, refrigerator,
electric iron etc.

70
 Electroplating of Cu
• For electroplating of Cu on metal surface,
• Electrolyte: (3-5%)H2SO4 / (15-30%) CuSO4
• Anode: Pure Cu metal or Graphite (inert)
• Cathode: Metal to be coated
• Additive: Boric acid or gelatin
Ionization reaction of electrolyte is observed,
CuSO4 Cu2+ + SO42- H2SO4 2H+ + SO42-

On passing current, Cu2+ + 2e- Cu (at cathode)

SO42- SO4 + 2e- (at anode)
Due to common ion effect, the ionization rate of Cu2+ is controlled
and the deposition process can also be controlled, with a current
density of 0.5 to 1.5 ampere/dm2. 71
 Factors affecting electroplating
• Surface cleaning – for strong adherent
• Concentration of electrolyte.
• Conductivity and stability of electrolyte
• Thickness of the deposit – for decorative purpose
thin coating and for corrosion protection multiple
coating.
• Current density (current per unit of the base metal)
should be low for uniform controlled deposition
• Additives: Ensure strong adherence and mirror
smooth coating.
• pH of the electrolytic bath
72
 Thin-Film Coatings
• PVD Coating (Physical Vapor Deposition)
• CVD Coating (Chemical Vapor Deposition)

73
 PAINTS

DEFINITION

Paint is a mechanical dispersion of one or

more finely divided pigments in a medium
(thinner + vehicle).

When a paint is applied to a metal surface,

the thinner evaporates, while the vehicle
undergoes slow oxidation forming a
pigmented film.
CHARACTERISTICS OF A GOOD PAINT

It should spread easily on the metal

surface.
It should have high hiding power.
It should not crake 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 glossy film.
 CONSITITUENTS OF PAINTS

Paint essentially consists of the following

Ingredients,
1. Pigments
2. Vehicle or drying oil
3. Thinners
4. Drier
5. Fillers or extenders
6. Plasticisers
7. Antiskinning
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 PIGMENTS
Pigment is a solid and colour producing
substance which is an essential constituent
paint,

 The functions of a pigment are

 To provide capacity, strength, desired colour
and give aesthetical appeal to the paint film.
 To give resistance against UV-light, abrasion,
wear, etc
 To improve the impermeability of paint film
from moisture and increase weather
resistance.
 THE MOST COMMONLY USED PIGMENTS
ARE,
• White pigments: white lead, Zn,
lithophone.
• Black pigments: Lamp black, Carbon
black
• Red pigments: Venetian red, Indian red,
Chrome red and Red lead.
• Blue pigments: Prussion blue.
• Green pigments: Chromium oxide.
• Yellow pigments: Chrome yellow and
Zinc yellow.
 VEHICLE OR DRYING OILS
1. It is film forming constituents of he paint .
These are glyceryl esters of high molecular
weight fatty acids present in animal and
vegetable oils.

FUNCTIONS:
They form a protective film by the
oxidation and polymerisation of the oil.
They hold the pigment particles together
on the metal surface.
They impart water repellency, toughness
and durability to the film.
Examples : Linseed oil, Soyabeen oil,
Dehydrated castor oil, Tung oil, etc.
 THINNERS (or) SOLVENTS
Thinners are added to the paint to reduce the
consistency or viscosity of the paints, so that they
can be easily applied to the metal surface. Thinners
are highly volatile solvent.

FUNCTIONS
 They reduce the viscosity of the paint.
 They dissolve the oil, pigments, etc. and produce a
homogeneous mixture.
 They increase the elasticity of the film.
 They evaporate readily and help the drying of the
film.
 They increase the penetrating power of the vehicle.
Ex: Turpentine, petroleum sprit, kerosene, xylol, etc.
 DRIERS
Driers are used to accelerate or catalysing of
the oil film by oxidation, polymerization and
condensation.

The main functions of drier is to improve the

drying quality of the oil-film.

Examples: Resonates, Linoleates, Tungstates

and Napthenates of Cobalt, Lead, Manganese
and Zinc.
 FILLERS (or) EXTENDERS

Fillers are added to the paint to reduce

the cost and increase the durability of the
paint.
FUNCTIONS
1. They reduce the cost and increase the
durability of the paint.
2. They serve to fill the voids of the paint
film.
3. They help to reduce the cracking of
paint.

Examples: Calcium carbonate, China

clay, gypsum etc.
 PLASTICISERS
Plasticisers are chemical added to the
paint to give elasticity to the film and
to prevent cracking of the film.
Ex: Triphenyl phosphate, Tributyl
phthalate, etc.

ANTISKINNING AGENTS
They are chemicals added to the paint
to prevent gelling and skinning of the
paint film.
Important antiskinning agents are
Polyhydroxy phenols.
 Special Paints
• Fire retardant paints
• Water repellant paints
• Temperature-indicating paints
• Heat resistant paints
Surface Preparation for Metallic Coatings
• Solvent cleaning
• Alkali cleaning
• Acid cleaning
• Mechanical cleaning
• Flame cleaning
• Sand-blasting 84
 Electroless Plating
• Electroless plating is defined as the controlled
auto catalytic deposition of a continuous film
by the interaction of a solution of a metal salt
and a chemical reducing agent.
• The reducing agent reduces the metallic salt
to metal, which gets deposited over the
catalytically activated surface giving a
uniform thin coating.

Metal salt + Reducing agent Metal + Oxidized products

85
 Various Steps of Electroless Plating

Step 1: Pretreatment and activation of the surface:

(i) Treatment with an organic solvent followed by

conditioning or etching by dipping, in a bath of
acid.
(ii) Activation by immersion in a colloidal solution of
tin or palladium. This yields a thin layer of Pd or Sn
on the treated surface.
(iii) A thin layer of the metal to be plated or anyother
suitable metal is electroplated on the surface of the
object.

86
Step 2: Preparation of plating bath:
The ingredients in the plating bath are,
(i) Coating metal: Soluble salt of the metal to be
deposited. (E.g., chlorides and sulphates)
(ii) Reducing agent: It reduces the metal salt to metal
(E.g., Formaldehyde, hyppphosphite etc.)
(iii) Exaltant: It enhances the plating rate.
(E.g., Succinate, fluoride etc.)
(iv) Complexing agent: It improves the quality of the
deposit.
(E.g., Tartrate, citrate, succinate etc.)
(v) Stabilizers: Stabilizers prevent the decomposition of
the plating bath solution.
(vi) Buffer solution: It is added to control the pH of the
bath. (E.g., CH3COONa, NaOH + rochelle salt) 87
Step 3: Procedure:

The object to be placed is cleaned and activated and

then immersed in the bath containing the salt of the
metal, reducing agent, exaltant, complexing agent,
stabilizer and buffer solution. The metal salt is
reduced to the corresponding metal.

Example: Electroless Nickel Plating

88