Department of Chemistry

Chemistry

UNIT III
CORROSION AND ITS CONTROL
Corrosion:-
It is defined as the destruction (or) deterioration and loss of solid metallic material by a
chemical (or) electrochemical attack by the environment.
Types of Corrosion:
There are two types of corrosion,
i) Dry Corrosion (or) Chemical Corrosion
ii) Wet Corrosion (or) Electrochemical Corrosion
DRY CORROSION:-
This type of corrosion is due to the chemical reaction of gases like oxygen, sulphur vapour,
halogens with metals or alloy surfaces. There are 3 main types of chemical corrosion.
a) Corrosion due to Oxygen (or) Oxidation Corrosion
Oxidation occurs at the surface of the metal and a metal oxide layer / scale is formed on
the metal. This layer forms a barrier that tends to prevent further oxidation. The reactions in the
oxidation corrosion are:
2M → 2Mn+ + 2 ne- [Loss of electrons]
Metal ions
2O2 + 2 ne → -
2nO2- [Gain of electrons]
Oxide ions
2M + nO2 → 2Mn+ + 2nO2-
Metal Oxide
For oxidation to continue
either the metal must diffuse outer
through the layer to the surface (or) the
oxygen should diffuse inwards through
the oxide layer to the metal.
Both the transfer occurs, but
outward diffusion of the metal is
generally much more rapid than the
inward diffusion of oxygen because the
metal ions is appreciably smaller than the
oxygen ion and also have higher
mobility.
Oxidation corrosion is brought about by the direct action of oxygen at low or high
temperature on metals in the absence of moisture. Alkali metals [Li, Na, K….] and alkaline earth
metals [Mg, Ca, Sn, ….] are readily oxidized at low temperature. At high temperatures, almost
all the metals except Au, Ag, Pt are oxidized.
Nature of Oxide film:
In dry corrosion, metal oxide is formed on the metal surface. The nature of the oxide film
decides further corrosion.
i) If oxide layer is stable and nonporous, it forms a protective coating and further corrosion is
prevented. Eg: Oxide film of Al, Sn, Pb, Cu etc.,
ii) If the layer is unstable, the oxide layer formed decomposes back into metal and oxygen. So
oxidation corrosion is not possible in this case. Eg: Ag, Au, Pt do not undergo oxidation
corrosion.

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iii) If the oxide film is porous, corrosion continues till the entire metal is converted into its
oxide. Eg: Oxides of Alkali and Alkaline Earth metals.
iv) If the oxide film is volatile, the oxide layer volatizes as soon as it is formed. This causes
rapid and continuous corrosion. [rate of corrosion is high] Eg: MoO3 is volatile.
Pilling – Bedworth Rule:
The protective and non – protective nature of the oxide film is determined by the rule called
Pilling – Bedworth rule. According to it, “If the volume of the oxide layer is higher than the
volume of the metal, then the oxide layer is protective and non porous”. On the other hand, “If
the volume of the oxide layer formed is lesser than the volume of the metal, then the oxide layer
is non-protective and porous”. Eg: Alkali – Alkaline earth metals forms oxides whose volume is
lesser than the volume of the metal.
b) Corrosion by other gases like SO2, CO2, Cl2, H2S, F2 etc.
The extent of corrosive effect depends mainly on chemical affinity between the metal
and gas involved. The degree of attack depends on the formation of protective and non-
protective film on the metal surface
i) If the film formed is protective / non-porous, the intensity of attack decreases. Eg: Chlorine
and Iodine attack silver forming a protective film of silver halide on the surface.
ii) If the film formed is porous / non protective, the surface of the whole metal is gradually
destroyed. Eg: Dry Chlorine attacks tin forming volatile SnCl4 there by leaving fresh metal
surface for further corrosion.
c) Liquid metal Corrosion:
It is due to chemical action of flowing liquid metal at high temperature on solid metal /
alloy such corrosion occur in devices used for nuclear power. The corrosion reaction involves
either (i) dissolving of solid metal by a liquid metal (or) (ii) Internal penetration of the liquid
metal into the solid metal. Both these modes of corrosion causes weak of the solid metal

WET CORROSION:
This type of corrosion occurs, i) When a metal comes in contact with the conducting
liquids. ii) When two dissimilar metals are either immersed or dipped partially in a solution. This
corrosion occurs, due to the existence of separate ‘anodic’ and ‘cathodic’ parts, between which
current flows through the conducting solution.
At anodic area, oxidation reaction takes place, so anodic metal is destroyed by either
dissolving or assuming combined state. Hence, corrosion always occurs at anodic areas. On the
other, at cathodic areas, reduction reaction takes place. Usually, Cathode reactions do not affect
the cathode, since most metals cannot be further reduced. The metallic ions (at anodic part) and
non metallic ions [at cathodic part] diffuse towards each other through conducting medium and
form a corrosion product somewhere between anode and cathode.
The electrons set free at the anode flow through the metal and are finally consumed in the
cathodic reaction. Thus, that electrochemical corrosion involves, (i) the formation of anodic and
cathodic areas or parts in contact with each other, (ii) presence of a conducting medium, (iii)
corrosion of anodic areas only and (iv) formation of corrosion product somewhere between
anodic and cathodic areas.
Mechanism of Wet Corrosion:
The corrosion of metals in aqueous solution is an electrochemical phenomenon. The anodic
reactions are the dissolving of the metal as metal ions. The cathodic reaction may involve either

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evolution of hydrogen gas (or) adsorption of oxygen depending on the nature of the corrosive
environment.

(i) Hydrogen evolution at the cathode:

Anode Reaction: Corrosion occurs in acidic
environment. The anodic reaction involves in
dissolution of metals as corresponding metallic
ions with the liberation of free electrons.
M → M2+ + 2e-

Cathode Reaction: The Cthodic reaction

consumes electrons from the metal and to
cathode, where H+ ions are eliminated as H2 gas
2H+ + 2e- → H2
Net Reaction: M+2H+→M2++ H2
In the hydrogen evolution type, the anodes are usually very large areas and the cathodes are
small points.
Eg., Fe → Fe2+ + 2e- ---------- Oxidation Reaction
2H+ + 2e- → H2 ----------- Reduction Reaction
Fe + 2H+ → Fe2+ + H2 ---------- Overall Reaction

Thus, this type of corrosion causes “displacement of hydrogen ions from the acidic solution by
metal ions”. Consequently, all metals above hydrogen in the electrochemical series have a
tendency to get dissolved in acidic solution with simultaneous evolution of hydrogen.

(ii) Oxygen absorption at the cathode:

Rusting of iron in neutral aqueous solution of electrolyte in the presence of atmosphereic
oxygen is a common example of this type of corrosion. The surface of iron is usually coated with
thin film of iron oxide. However, if this iron oxide film develops some cracks, anodic areas are
created on the surface, while the well metal parts acts as cathodes. It follows that the anodic
areas are small surface parts, while nearly the rest of the surface of the metal forms large
cathodes.
The anodic reaction of the metal is the
dissolving of iron metal to form Fe2+ ions.
Fe → Fe2+ + 2e-
On the cathodic area, the electrons flow from
the anodic part to the cathodic part. They combine
with the dissolved oxygen in the presence of
water to form hydroxide ions.
1/2O2 + H2O + 2e- → 2(OH)-
The Fe2+ ions [at anode] and OH- ions [at
cathode] diffuse and when they meet, ferrous
hydroxide is easily oxidized to ferric hydroxide is precipitated.
Fe2+ + 2OH- → Fe(OH)2 
(i) If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide.
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3
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This product, called yellow rust, actually corresponds to Fe2O3. H2O

(ii) If the supply of oxygen is limited, the corrosion product may be even black anhydrous
magnetite, Fe3O4.
Corrosion occurs at the anode; the smaller Fe2+ ions diffuse more rapidly than the larger
OH- ions. So, the rust is deposited at the cathode.

Galvanic Corrosion:
When two dissimilar metals [eg: Zn & Cu] are electrically connected and exposed to an
electrolyte, the metal higher in electrochemical series undergoes corrosion. This type is called
galvanic corrosion.
Eg.: Zn [higher in electrochemical series] forms the anode and is attacked and get dissolved,
whereas Cu [lower in electrochemical series or more noble] acts as cathode.
Mechanism:
In acidic solution, the corrosion occurs by the
hydrogen evolution process, while in neutral or
slightly alkaline solution oxygen absorption occurs.
The electron current flows from the anodic metal, Zn
to the cathodic metal Cu.
Zn → Zn2+ + 2e- (Oxidation)
Thus it is evident that the corrosion occurs at
the anodic metal, while the cathodic part is protected
from the attack.

Differential Aeration Corrosion:

This is the most common type of
concentration cell corrosion and it occurs when
one part of the metal is exposed to a different air
concentration from the other part of the metal.
This causes a difference in potential between
differently aerated areas. The differential
aeration accounts for the corrosion of metals
partially immersed in a solution just below the
water level. This is also known as “Water Line
Corrosion. Eg., A Zn rod immersed partially in a
NaCl solution.
The parts above and closely adjacent to the water line are more strongly aerated because
of the easy contact with oxygen and hence become the cathode. On other hand, parts immersed
to greater depth which have less access to oxygen becomes the anode. So, a difference of
potential is created, which causes a flow of current between the two differentially aerated areas
of the same metal. Zn will dissolve at the anodic areas and oxygen will take up electrons at the
cathodic areas to form hydroxyl ions.
Zn → Zn2+ + 2e- (Oxidation) Anodic reaction
½ O2 + H2O +2e → 2OH
- -
(Reduction) Cathodic reaction
The circuit is completed by migration of metallic ions through the electrolyte and the flow of
electrons, through the metal from anode to cathode.

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Factors Influencing Corrosion:

The rate and extent of corrosion depends the following factors.
1) Nature of the Metal:
i) When two metals are in contact the rate of corrosion depends on the difference in their
electrode potentials. The greater the difference, faster is the corrosion of anode metal.
ii) Corrosion is more rapid, if the anodic area is small.
iii) Impurities in a metal increase the corrosion rate, pure metal resist corrosion.
iv) The rate of corrosion depends on the physical state of the metal such as gain size etc,.
The smaller the grain size, greater will be its corrosion.
v) The ratio of volume of the metal oxide to the metal is known as “specific volume
ratio”. Greater the specific volume ration, lesser is the corrosion ration.
vi) Metals like aluminium (Al), Cr, Mg, Ni & Co are passive and they exhibit higher
corrosion resistance. A highly protective thin film of the oxide is formed on these metals.
vii) If the corrosion product is soluble in the corroding medium, then corrosion proceeds
at a faster rate.
viii) If the corrosion product is volatile then more corrosion will occurs.
2) Nature of the corroding environment:
i) Increase in temperature increases corrosion reactions.
ii) Humidity in air increases corrosion rate.
iii) Impurities such as CO2, H2S, SO2, HCl, H2SO4 vapours in the atmosphere increase the
corrosion rate.
iv) Generally, acidic media [pH less than 7] are more corrosive than the alkaline and
neutral media.
v) Presence of anions like silicate prevents further corrosion. Anions like chlorides,
increases the corrosion.
vi) Higher the conductance of the corroding medium, sever is the corrosion.
vii) Higher the supply of oxygen (or) air, higher is the corrosion rate.

Corrosion Control (or) Methods of Prevention of Corrosion:

Some of the corrosion control methods are described as follows:
1. Proper Designing:
The design of the material should be such that “Corrosion even if it occurs, is
uniform and does not result in intense and localized corrosion”. The important design
principles are:
i) The contact of dissimilar metals in the presence of a corroding solution is avoided.
ii) When two dissimilar metals are to be in contact, the anodic material should have as large
area as possible and the cathodic material should have as small as possible.
iii) If two dissimilar metals in contact have to be used, they should be as close as possible to
each other in the electrochemical series.
vi) Insulating fitting may be applied in between the dissimilar metals to avoid direct metal-
metal electrical contact.
v) The anodic metal should not be painted or coated, because any break in coating would
lead to rapid localized corrosion.
vi) Prevent the occurrence of inhomogeneities, both in the metal and in the corrosive
environment. Thus, a proper design should avoid the presence of crevices between adjacent

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parts of the structure. It should be replaced by weld joints, whereas bolts and rivets are
undesirable for reduce crevices.
vii) The design should allow for adequate cleaning and flushing of the critical parts of the
equipment. Sharp corners and recesses should be avoided, because they favour the formation
of stagnant areas and accumulation of solids etc.
viii) The equipment should be supported on legs to allow free circulation of air and prevent
formation of stagnant pools (or) damp areas.
ix) By using pure metal, corrosion resistance is increased.
Different types of Joints

2. Cathodic Protection:
The reduction or prevention of corrosion by making metallic structure as
cathode in the electrolytic cell is called cathodic protection. There are two methods of
applying cathodic protection to metallic structures.
i) Sacrificial Anodic protection (Galvanic protection) [SAP]
ii) Impressed Current Cathodic Protection [ICCP]

i) Sacrificial Anodic protection (Galvanic protection) [SAP]

In this method, the metallic structure to be protected is made of cathode by connecting it
with more active metal [anodic metal]. Hence all the corrosion will concentrate only on the
active metal. The parent structure is thus protected. The more active metal so employed is
called sacrificial anode. The
corroded sacrificial anode block is
replaced by a fresh one. Metals
commonly employed as sacrificial
anodes are magnesium, Al, Zn and
their alloys. Magnesium has the most
negative potential [-2.40 V] and can
provide highest current output and
hence is widely used in high
resistivity electrolytes like soil.
3.

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Important applications of sacrificial anodic protection are:

i) This method is used to protect ships and boats from marine corrosion. Sheets of Zn or Mg
are hung around the hull of the ships. They act as anode compared to iron metal of the ship.
Hence, corrosion concentrates on Zn or Mg. They are thus, sacrificed to save iron. They are
called sacrificial anodes.
ii) Protection of buried pipelines, underground cables from soil corrosion.
ii) Protection from merine corrosion of cables, pipes etc.
iv) Insertion of magnesium sheets into the domestic water boilers to prevent the formation of
rust. v) Ca metal is employed to minimize engine corrosion.
Advantages:-
1. Low installation and operating cost.
2. Capacity to protect complex structures
3. Applied to wide range of severe corrodes.
Limitations:-
1. High starting current is required.
2. Uncoated parts cannot be protected.
3. Limited driving potential. So it is not applicable for large objects.
4. Anodes should be changed periodically.

ii) Impressed Current Cathodic Protection:-

In this method, an impressed current is
applied in opposite direction to nullify the
corrosion current and convert the corroding metal
from anode to cathode. Usually the impressed
current is derived from a direct current sources
[like battery or rectifier on A.C line] with an
insoluble, inert anode [like graphite, platinum,
stainless steel].
A sufficient D. C. current is applied to an
inert anode buried in the soil [or immersed in the
corroding medium] and connected to the metallic
structure to be protected. The anode is usually a
back fill, composed of coke, breeze or gypsum.
So as to increase the electrical contact with the
surrounding soil it is used. It can be applied to
open water box coolers, water tanks, buried oil
or water pipes, condensers, transmission line
towers, marine pipes, laid up ships etc.
Limitations:
i. Costly method
ii. Failure method when current is switched off /
cut off.

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3. Use of inhibitors:
A corrosion inhibitor is a substance which are added in small quantities to the
aqueous corrosive environment, effectively decreases the corrosion of a metal. They form a
protective layer on the cathodic and anodic areas. There are two types of inhibitors are anodic
and cathodic inhibitors.
i. Anodic Inhibitors:
These inhibitors are those that stifle the corrosion reaction, occurring at the anode,
by forming a sparingly soluble compound with a newly produced metal ion. They are absorbed
on the metal surface, forming a protective film or barrier, thereby reducing the corrosion rate.
The substances used are chromates, phosphates and tungstates of transition elements with
higher oxygen content.
ii. Cathodic Inhibitors:
Depending upon the environment, we have to use different cathodic inhibitors.
a) In acidic solution, the main cathodic reaction is evolution of hydrogen,
2H+ + 2e- → H2
By adding cathodic inhibitors, the diffusion of H+ ions is decreased. So, the above
reaction will not take place. The substances added are organic inhibitors [like amines, ureas,
thioureas, mercaptans, etc.,] which are capable of being absorbed at the metal surfaces.
b) In neutral solution, the cathodic reaction is,
1/2O2 + H2O + 2e- → 2(OH)-
The corrosion is controlled by eliminating oxygen from the corroding medium or by
retarding its diffusion to the cathodic areas. The former is usually attained by adding reducing
agents like Na2SO3 or by deaeration. The inhibitors like Mg, Zn or Ni salts to the environments
are used in the latter case. These react with hydroxyl ions forming corresponding insoluble
hydroxides, which are deposited on the cathode forming more or less impermeable self-barriers.

Protective Coating: Coatings are given to a surface – i) to protect it from corrosion,

ii) to give a pleasing (or) decorative appearance.
Coatings are divided into two types. They are Organic coating and Inorganic coating
i) Organic Coating: eg: Paints, Varnishes, Thinners
ii) Inorganic Coating – There are two types , they are
1) Metalli Coating: It is further divided into two types, they are
i) Anodic Coating
ii) Cathodic Coating
2) Non-metallic Coating: It is further divided into three types, they are
i) Anodising Coating
ii) Phosphate Coating
iii) Oxide Coting
iv) Chromate Coating
Methods of application of metallic coating have five methods:
i) Hot dipping Process – a) Galvanising and b) Tinning
ii) Cementation process – a) Sherardising, b) Chromising and c) Colorising
iii) Cladding process
iv) Electroplating (or) Electrodeposition
v) Metal Spraying

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Inorganic Coatimg
1) Metallic Coating:
In metallic coating, one metal surface is coated with another metal. The metal to be
coated is base metal. The metal used for coating is called coat metal. There are two types.
a) Anodic Coatings are produced from coating – metals, which are anodic to the base
metal. In this, the electrode potentials of the base metals are higher and the electrode
potentials of the coat metals are lower. If any crack occurs on the surface of the coat
metal, then galvanic cell is formed between the coat metal and exposed area of the
base metal. Eg,. Coating of Zn, Al & Cd on steel are anodic, because their electrode
potentials are lower than that of the base metal iron.
In case of galvanized steel, Zn coating-metal (anode) is attacked, leaving underlying
cathodic base metal (iron). Thus, no attack on iron, until practically all the Zn has first
corrected in vicinity of the exposed iron spot. So, Zn coating protect iron sacrificially. [eg,.
Zn on Iron, Anodic coating protects the underlying base metal “Sacrificially”. Electrode
potential of coating metal is lower than base metal. If pores, breaks or discontinuities occur
in such coating, base metal is not corroded till all coating metal is consumed.]
b) Cathodic Coatings are obtained by coating a more noble metal [having higher
electrode potential] than the base metal, because they have higher corrosion resistance
than the base metal. Cathodic coating provides effective protection to the base metal
only when they are completely continuous and free from pores, breaks or
discontinuities. Eg,. A tin coating on a sheet of iron provides protection only as long
as the surface of the metal is completely covered, since tin is lower than iron in
electromotive series.
[eg,. Sn on iron, Cathodic coating protects the underlying base metal, due to its noble
character and higher corrosive resistance. Electrode potential of coating is higher than base
metal. If pores, breaks or discontinuities occur in such coating, the corrosion of the base
metal is speeded up.]
2) Non-metallic coating – not in our syllabus

Methods of application of metallic coating have five methods:

1) Hot dipping Process
It is used for producing a coating of low-melting metal such as Zn, Sn, Pb, Al etc
on iron, steel, copper, which have relatively higher melting points. The process in
general, consists of immersing the base metal in a bath of the molten coating – metal,
covered by a molten flux layer [ZnCl]. The flux cleans the base metal surface and
prevents the oxidation of the molten coating – metal. For good adhesion, the base metal
surface must be very clean; otherwise it cannot be properly wetted by the molten metal.
Two most widely applied hot dipping methods are a) Galvanising and b) Tinning
a) Galvanising:
It is a process of coating iron sheet with a thin coat of Zn to prevent them from
rusting. The galvanizing process consists of following processes.
(i) Pickling treatment: The iron article is first pickled in a pickling solution
containing 7% of H2SO4 at 60˚ - 90˚C. This is done for above 15 to 20 min. This
treatment removes any scale, rust and impurities.

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(ii) Preliminary treatment: Here, the article is treated with 5% HF to dissolve the
grains of the sand etc., on the surface of the metal. After this treatment, it is stores
under water to prevent oxidation.
(iii) Cleaning chamber: To clean any oxide layer on the surface of the article, it is
passed through the drying chamber by the hot air. Thus article is dried.
(iv) Zinc bath treatment: It is then dipped in bath of molten zinc, maintained at 425 -
450˚C. The surface of the bath is covered with ammonium chloride flux to
prevent any oxide formation. When the article is taken out, it is found to have
been coated with a thin layer of Zn. It is then passed through a pair of hot rollers.
This process removes any superfluous [excess] of Zinc and produces a thin film
of uniform thickness. Then, it is annealed at a temperature of 650˚C and finally,
cooled slowly.

NOTE : Diagram refer class work

Uses: Roofing sheets, wires, pipes, nails, bolts, screws, buckets, tubes etc.
b) Tinning:
Tinning is mostly done on the mild steel plates for the requirements of food stuff
industry. Tin is less electropositive so care should be taken to cover the surface of iron
completely.
In this process, the iron sheet is
first treated with dil. Sulphuric acid to
remove any oxide film. Then it is passed
through a molten flux like ZnCl2 and then
passed through a molten tin bath. The
ZnCl2 flux helps the molten metal to
adhere to the metal sheet. Then it is
passed through a suitable vegetable oil
like palm oil to prevent the hot surface
from oxidation. The squeezer removes the excess tin and produces a uniform film on the iron
sheet. The tin coating is resistant to the atmosphere and it is non-toxic. It is used for steel and
copper metals. This coating is done for containers used for storing food materials like ghee,
oils, pickles etc.

2) Cementation Process:
In cementation, the base metal is heated with the coating metal in the form of fine
powder in order to promote the diffusion of the coating metal into the base metal. The
coatings obtained are of uniform thickness.
The base metal is generally steel and the coating metals used is zinc, chromium
and aluminium. When the coating metal is zinc, the process is called sherardizing. When

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the coating metal is chromium, the process is called chromizing. When the coating metal
is aluminium, the process is called calorizing.
i) Sherardizing:
Cementation with zinc powder is called sherardizing in honour of Sherard
Cowpercoles who developed the process in 1900. The base metal is heated with zinc dust
in a metal drum maintained at a temperature of 350 - 370˚C. The drum is closed tightly
and rotated with constant heating for two to three hours. During this process zinc gets
diffused ino iron forming an alloy of Fe-Zn on the surface. Sherardized coatings are used
for protecting small steel parts such as nuts and bolts against atmospheric corrosion.
ii) Chromizing:
The base metal is heated with a powdered mixture of 55 per cent chromium and
45 per cent alumina at a temperature of 1300 - 1400˚C for about 3-4 hours in a closed
drum. The purpose of using alumina is to prevent the coalescing of chromium particles.
The outermost surface of the base metal is converted into a chrome alloy which protects
the metal against corrosion. This method is used to protect gas turbine blades.
iii) Calorizing:
Here the base metal is heated with a powdered mixture of aluminium and alumina
in a drum at a temperature of 840 - 930˚C for 4 – 6 hours. Calorized steel is used for
making furnace parts.

3) Cladding Process:
Cladding is a method by which the surface to be protected is sandwiched between
two layes of the coat metal and pressed between rollers. The clad metals used are
aluminium, chromium and nickel. Copper-clad steel is used in the electrical industry,
because this kind of steel has good electrical conductivity and high strength.

4) Electroplating or Electrodeposition:
Electroplating is a process in which metals are deposited or plated on base metals
from solutions containing metallic ions by means of electrolysis. The objectives of
electroplating are as follows:
1. To obtain improved resistance to corrosion and chemical attack.
2. To get better appearance
3. To get increased hardness
4. To change the surface properties of metals and non-metals
In the electroplating process, the freshly cleaned base metal which is to receive the
coat is made the cathode in a suitable electrolyte bath
containing (a) a solution of the salt of the metal to be
electrodeposited, (b) buffer solution to control the pH, and
(c) additional reagents to enhance conductivity and to aid
the formation of smooth, dense and coherent coating.
The concentration of the salt solution is maintained
by the addition of the metal salt at regular intervals or by the
use of continuously dissolving anode of the metal. The
plating is usually done at a high current density. The nature of the deposit depends upon the
current density, pH and the concentration of the bath. A typical electroplating process is
shown in figure.

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The various types of electroplating are as follows.

a) Chromium Plating: Protecting iron, chromium plating is widely adopted. A warm bath
of chromic acid and a high current density with appropriate temperature are used. The
anode is lead and the cathode is the base metal to be plated. Chromium coats give an
excellent shining appearance and are stable because of the formation of an invisible,
strongly, adherent protective layer of Cr2O3 on exposure. However, Chromium coats are
porous and contain fine cracks. Hence the article to be chromium plating is given a
copper coating to give protection from corrosion which is then nickel plated. Chromium
is finally placed on the nickel coat.
b) Nickel Plating: A bath of nickel sulphate and nickel chloride is used. A pure nickel sheet
is used as anode and the base metal as the cathode. Nickel coats are not quite stable; the
highly polished surface deteriorates with age with the appearance of rust spots.
c) Copper Plating: A bath of acidified copper sulphate solution and copper anode are used.
The base metal is used as the cathode. Copper plating is used in printed circuit boards. It
is coated at the bottom of the stainless steel cooking utensils to affect better heat transfer.
d) Gold Plating: Double cyanide of gold and potassium is used as the electrolytic bath. A
pure gold plate is used as the anode and the base metal as the cathode. It is used for high
quality decoration and high oxidation-resistant coatings.

5) Metal Spraying:
In spraying, the molten coat metal is sprayed over the base metal using a spray
gun. The metal thus sprayed adheres to the base metal surface. The coating formed is
continuous but porous. This method is used for applying coatings of copper, lead, nickel,
etc. This method can be applied to finished structures such as bridges, tanks and ships.

Organic Coatings:
Organic coatings are inert organic barriers applied to the surface of base metals for
corrosion resistance and decoration. Paints, varnish, lacquers and enamels are the main organic
coatings.

Paints:
Paint is a viscous suspension of finely divided solid pigments in a fluid medium which on
drying yields an impermeable film having considerable hiding power. When paint is applied to a
metal surface, the thinner evaporates, while the drying oil slowly oxidizes forming a dry
pigmented film.
Requirements of a good paint:
A good paint should essentially have the following:
1. A good paint should form a good impervious and uniform film on the metal surface.
2. It should have a high hiding (covering) power.
3. The film should not crack on drying.
4. A good paint should adhere well to the surface.
5. It should spread on the metal surface easily.
6. It should give a glossy film.
7. It should be corrosion resistant.
8. A good paint should give a stable and decent colour on the metal surface.

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Constituents of paint and their functions:

The important constituents of paint are as follows:
1. Pigments
2. Vehicle or drying oils or medium
3. Thinners
4. Driers
5. Fillers of extenders
6. Plasticizers
7. Antiskinning agents
Pigments: A pigment is a solid and colour producing substance in the paint.
Characteristics: A pigment should have the following characteristics:
a) A pigment should be chemically inert
b) It should be non-toxic
c) It should be opaque and possess high covering power
d) A pigment should be cheap and easily available
e) It should mix freely with film forming constituents of the oil
The most commonly used pigments are as follows:
a) White pigments – White lead, BaSO4 and TiO2
b) Blue pigments – Prussian blue and ultramarine blue
c) Black pigments – Graphite and carbon black
d) Red pigments - Read lead and Fe2O3
e) Green pigments - Chromium oxide
f) Brown pigments - Iron containing clays
g) Yellow pigments - Chrome yellow and Zinc yellow
Functions: The following are the functions of the pigments
a) A pigment gives opacity and colour to the film
b) It provides an aesthetic appeal to the film
c) A pigment gives strength to the film
d) It protects the film by reflecting the destructive ultraviolet rays
Vehicle or drying oil or medium: The liquid portion of the paint in which the pigment is
dispersed is called a medium or vehicle. This is the film forming constituent of the paint.
Vehicles are high molecular weight fatty acids present in animal and vegetable oils, e.g. linseed
oil, dehydrated castor oil, soyabean oil and fish oil.
Functions: The following are the functions of vehicles:
a) Vehicles hold the pigment particles together on the metal surface
b) They form the protective film by evaporation or by oxidation and polymerization of the
unsaturated constituents of the oil
c) Vehicle give better adhesion to the metal surface
d) They impart water repellency, durability and toughness to the film.
Thinners: Thinners are added to paints to reduce the consistency or viscosity of the paints so
that they can be easily applied to the metal surface. Thinners are volatile in nature and evaporate
easily after application of the paint, e.g. turpentine and petroleum spirit.
Functions: The following are the functions of thinners:
a) Thinners reduce the viscosity of the paint to render it easy to handle and apply to the
metal surface.
b) They dissolve the oil, pigments, etc. and produce a homogeneous mixture

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c) Thinners evaporate rapidly and help the drying of the film

d) They increase the elasticity of the film
e) Thinners increase the penetrating power of the vehicle
Driers: Driers are used to accelerate or catalyze the drying of the oil film by oxidation,
polymerization and condensation, e.g. naphthenates, borates and tungstates of lead, cobalt and
manganese.
Functions: Driers act as oxygen carrier catalysts which help the absorption of oxygen and
catalyze the drying of the oil film by oxidation, polymerization and condensation.
Fillers or Extenders: Fillers are used to reduce the cost and increase the durability of the paint,
e.g. talc, china clay, calcium sulphate and calcium carbonate.
Functions: The following are the functions of fillers:
a) Fillers serve to fill the voids in the film
b) They reduce the cracking of the paints
c) Fillers increase the durability of the paints
d) They reduce the cost of the paint
Plasticizers: Plasticizers are chemicals added to paints to give elasticity to the film and to
prevent cracking of the film, e.g. triphenyl phosphate and tricresyl phosphate.
Antiskinning agents: They are chemicals added to the paint to prevent skinning of the paint, e.g.
polyhydroxy phenols.

Mechanism of drying oils:

Drying oils are the film forming constituents of the paint. These are fatty oils which are
extracted from plants or animals. The fatty oils are tri-esters of glycerol:

The oil film after it has been applied to the protected surface absorbs oxygen from air at the
double bonds forming peroxides which isomerizes, polymerize and condense to form a tough and
highly cross linked macromolecular film.

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Methods of application of paint:

Paint is applied to the surface by many methods. The important methods are given as follows:
1. Brushing: A surface may be painted using a brush. Brushes may be made according to
the type of paint applied
2. Spraying: Paint is sprayed on the surface by using a spray gun. The advantage of this
method is that is applied to the surface very quickly and easily. It is used for painting
articles such as automobiles and refrigerators.
3. Dipping: This method is applicable to articles which have got a uniform shape. The
articles to be coated are dipped in paint which is kept in a tank. Enameled wire is coated
by this method.
4. Roller Coating: Roller coating is applied when the article is in the form of flat sheets.
Sheet metal for containers is coated by this method.
5. Tumbling: Tumbling is applicable for small articles made of wood. The articles and the
paint to be applied are put into a barrel is rotated for a given period. The articles are then
put on drying trays for drying.

Failure of Paint
Paint may fail due to several reasons:
1. Chalking: Chalking is the gradual powdering of paint. It is caused by continuous
destructive oxidation of the oil after the original drying of paint.
2. Erosion: It is very quick chalking
3. Flaking: Flaking is caused due to poor adherence of a paint film to the surface because
of the presence of grease on the surface.
4. Checking: It is a very fine type of surface cracking.
5. Alligatoring: The centre portion of the film remains attached to the surface, whereas the
portion around the centre peels off.
The failure of paint can be prevented by the following ways:
1. Carefully preparing the surface before application of paint.
2. Applying a suitable primer coat.
3. Applying the paint evenly.
4. Allowing each paint coat to dry sufficiently before the next coat is applied.

Varnish
It is a homogenous, colloidal dispersion of natural or synthetic resins in oils or thinners or
in both. The film dries by evaporation, oxidation and polymerization to form a transparent, hard,
glossy and durable film. There are two types of varnishes are oil varnish and spirit varnish.
Oil Varnishes: They contain one or more natural or synthetic resins in a drying oil and a volatile
solvent. The oil reduces the neutral brittleness of the pure resins.
Spirit Varnishes: In this type, a resin is dissolved in a completely volatile solvent. It dries by the
evaporation of the solvent. The film is brittles so it will crack after some time.
Constituents of Varnishes:
1. Resins: They may be natural resins like “Shellac, rosin, copal” etc or synthetic resins like
phenol formaldehyde, urea formaldehyde etc., The resins provide hardening, resistant to
weather, durability, resistance to chemical action and water-proof.
2. Drying oils: They are like linseed oil, soyabean oil, tung oil etc. They dry by
polymerization, oxidation and condensation.

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3. Solvents or Thinners: They are like turpentine, kerosene, petroleum spirits, butyl and
ethyl alcohols, acetone etc. They reduce the viscosity of varnish.
4. Dryers: They are added to increase the drying rate of oil. E.g. resonates, naphthenates of
lead, cobalt and Manganese.
Uses: i) For the protection of articles against corrosion.
ii) As a brightening coat to the painted surface
iii) For improving the appearance and intensifying the ornamental grains of
wooden surfaces.

Emulsion Paints:
It is a dispersion of rubber like resin in water. In addition, it contains film forming vehicle
(oil), pigments and extenders. It may also contain stabilizers, preservative, driers and
antifoaming agents.
1. When emulsion paint is applied to a surface, water evaporates emulsion breaks and
oleoresinous particles coalesce to form a continuous, homogeneous and clear film.
2. Emusion coats are less odourless, non inflammable, quick drying and easier to apply than
ordinary paints.
3. The resultant paint film resembles the conventional paint film but is less water resistant.
Constituents of Emulsion paint:
1. Rubber like resin: semisolid polystyrene, polyvinyl acetate
2. Oleoresinous materials: Oil used is readily dispersible such as linseed oil.
3. Pigments: Mica and water dispersing like titanium dioxide
4. Extenders: Mica, silica, Clay, MgSiO3
5. Emulsifying agents: Used for dispersion of a) Rubber like materials is complex
phosphate like tetra sodium phosphates. b) Organic pigments are dioco sodium sulpho
succinate, sodium lauryl sulphate etc.
6. Emulsifying stabilizers: i) Proteins like dextrin, starch, water soluble gums, soya protein
atc, ii) Stabiliser imparts chemical resistance to the emulsions.
7. Preservatives are added to prevent the decomposition of any protein and to eliminate the
growth of fungus eg. Mercurie chloride, thymol and chlorothymol.
8. Antifoaming agents are added to check any excess foam formation by the agitation of
emulsion paints during their manufacture. Eg; Pine oil, Kerosene.
9. Driers are added to an emulsion paint which contains oxidisable oils. They are Co, Mn,
Zn resonates, phthalates, etc.

Special Paints:
1) Fire Retardant Paints:
These paints contain components which breakdown at high temperature and
produce a non-inflammable gas as CO2, water vapour, NH3, HCl etc. They cover the
flame and either extinguish or minimize the rate of burning. The paints containing poly
phenyl chloride, chlorinated rubber break down to give non-inflammable HCl gas, urea
formaldehyde gives NH3 gas, carbonated pigments gives CO2. The paints containing,
calcium ammonium phosphates, magnesium ammonium phosphate gives a glass like
structure that melts at higher temperature and forms a barrier between the air and the
inflammable substance and stops the combustion.

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2) Temperature Indicating Paints:

In furnaces, a special paint is used to indicate different temperature existing in the
heating zones by a colour change. The paint contains a special ingredient which
undergoes a colour change at e specific temperature.
The ingredient is a double-salt or amine salt of Cu, Iron, Cr, Mn, Co, Ni, Mo or a
combination of these salts. These paints are made at present to indicate any temperature
between 45˚C 1450˚C. These paint coatings are given at top coating of lacquer to protect
from the corrosive gases like H2S and SO2.
3) Anti-fouling Paints:
It is used in marine construction. They contain anti-fouling agents like mercuric
oxide, cuprous oxide, penta chloro phenol, phenyl mercury naphthanate. These retards
the fouling of ships etc by marine worms, fungi, etc and thus helping the control of
corrosion.
4) Luminescent Paints:
They contain luminiphore pigments which fluoresce under the influence of UV
light. Such pigments absorb UV radiations and emit radiations in the visible region of the
spectrum. Luminiphore pigments contain ZnSO4 or sulphides of Zn & Cd, Titania, with
small amounts of modifiers like Cu, Ag, Mn, & boron called activators. Here the day-
light colour is different from luminescent paint.
5) Water Repellant Paints:
The active ingredient used in these are silicones, cellulose dinitrate etc which are
water reppelant.

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