UNIT II

CORROSION AND CORROSION CONTROL

Introduction

Metals and alloys are generally used as fabrication or construction materials in engineering.
If the metal or alloy structures are not properly maintained, they get rusted slowly by the
action of atmospheric gases, moisture and chemicals. This phenomenon of deterioration or
destruction of metals and alloys is known as ‘corrosion’.

Corrosion is defined as the gradual degradation or deterioration of alloys by the chemical or

electrochemical reaction with its environment.

Reason for corrosion

Metals occur usually in two different forms. 1. Native state, 2. Combined state

1. Metals in Native state: the metals occur in native or free or un-combined states are non-
reactive with environment. They are noble metals; exist as such in the crust. They have very
good corrosion resistance.

Examples: Silver (Au), Platinum (Pt) and Gold (Ag).

2. Metals in mineral form

Other metals except noble metals are reactive to the atmosphere and form stable
compounds as their respective oxides, sulphides, chlorides and carbonates. Because they
exist in the form of stable compounds, they are called ores and minerals.

How and why corrosion occurs?

Most of the metals are extracted from their ores. During the process of extraction, the ores
are reduced to their metallic state. Therefore, this group of metals are in the oxidised state in
their ores. Hence, the reduced metallic state is unstable and tends to be in higher energy
state. Hence metals that are extracted from the ores are tending to reverse their process;
that is they form metal oxides from metallic state.

Therefore when these metals are used in various forms and exposed to environments such as
dry gases, moisture etc, the metal surface begins to decay which is known to be the basic
reason for the corrosion of certain metals. Examples: Copper, Iron and Aluminium.

Extraction
(Reduction)

Metal ore or metallic Metal

compounds Oxidation
Consequences of corrosion

Due to the formation of corrosion over the machinery, the efficiency of the machine gets
lost. The food products may get contaminated with rust. The life time of equipment or an
instrument is reduced.

Theories of corrosion

Based on the nature of the exposing environment, corrosion is classified in to two types

1. Dry or chemical corrosion and

2. Wet or electrochemical corrosion

Dry corrosion is due to the exposure of metal surfaces to gases such as oxygen, hydrogen
sulphide, sulphur dioxide, nitrogen etc.

There are three main types of dry corrosion based on the nature of gases that attack the
metal surface

1. Corrosion by oxygen or oxidation corrosion

2. Corrosion by hydrogen
3. Liquid metal corrosion

I. Oxidation corrosion or corrosion by oxygen

This type of corrosion occurs when the metal surface is exposed to oxygen at lower
temperature or at high temperature in the absence of moisture. Alkali metals (Li, K, Na) and
alkaline earth metals (Mg, Ca, Sn) are rapidly oxidised at lower temperature and all other
metals except noble metals (Au, Pt and Ag) are oxidised at higher temperature.

Rust
(Metal
oxide)
Metal Metal

A metal piece before Metal piece after exposure to

exposing to atmosphere atmosphere showing corrosion
product on the surface

Fig. 2.1 Corrosion of a metal piece

Mn+
O2-
e
Metal Mn+
e
O2- Atmosphere
Mn+
O2-
e

MO (Metal
i )
2
Mechanism of dry corrosion
Step1: when the metal is exposed to atmosphere the metal undergoes oxidation as a result
of which metal ion is formed

M Mn+ + ne-

Step 2: The atmospheric oxygen which is in contact with the metal surface gets converted in
to oxide ion (O2-) due to the transfer of electrons from metal

n/2 O2 + ne- nO2-

Step 3: The oxide ion produced at the surface of the metal combines with the metal ion to
form metal oxide film which grows on the surface

Hence the overall reaction is

M + n/2 O2 Mn+ + nO2-

Mn+ + nO2- MO

When the surface of the metal is covered by a single layer of metal oxide (ie. corrosion
product), further corrosion occurs by the diffusion of metal ions through metal oxide layer.
Initial corrosion occurs at metal atmosphere interface and subsequent corrosion occurs at
metal oxide and atmosphere interface by the diffusion of metal ions. Hence the corrosion
product growth is perpendicular to the surface of the metal piece as shown in Fig. 2.2

Atmosphere O2 O2

O2

1/2O2 + M MO Metal-oxide and atmosphere

interface
Corrosion product

Metal and Metal-oxide

interface

Metal

Fig. 2.2 illustration of corrosion process

Effect of nature of the corrosion product or metal oxide

3
The nature of the oxide film formed over the metal surface plays a vital role in oxidation
corrosion.

The types of oxides may be

1. Stable oxide layer

2. Unstable oxide layer
3. Volatile oxide layer
4. Protective or non protective oxide layer

1. Stable oxide layer

If the oxide layer formed on the top of the metal surface is fine grained and bound
tightly to the metal surface, then it is called stable oxide layer. Such layer is impervious in
nature and prevents further oxygen access through the oxide layer by diffusion. Such a film
acts as the protective film or protective layer and further corrosion does not occur.

Examples: Al2O3, SnO2, PbO2, CuO.

2. Unstable oxide layer

If the oxide layer formed on the surface of metal due to corrosion is converted back in to
metal and oxygen spontaneously, it is called unstable oxide layer.

Examples: PtO, AgO, AuO.

3. Volatile oxide layer

If the formed oxide layer is vaporised immediately after the formation leaving the metal
surface for further corrosion is called volatile oxide layer.

Examples: MoO3 (molybdenum trioxide).

4. Protective or non protective oxide layer (Pilling-Bedworth rule)

Pilling Bedworth rule is based on the volume of the corrosion product formed to the pure
metal ratio.

(a) According to pilling-Bedworth rule, if the specific volume of the oxide layer formed is
less than the volume of the metal then the oxide layer is called porous and non-
protective.

e.g The oxides of Na, Mg, Ca etc.,

(b) If the specific volume of the metal oxide layer formed is greater than the volume of
the metal then the oxide layer is called non-porous and protective.

Examples: Oxides of Al, Pb, Sn etc.

Pilling-Bedworth ratio

It is the ratio between the metal oxide formed due to corrosion and the
metal consumed for the formation of metal oxide.

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II. Corrosion by Hydrogen

(a) Hydrogen embrittlement (at room temperature)

When a metal piece exposed to gases like H2S at room temperature, atomic
hydrogen is released according to

Fe + H2S FeS + 2(H)

This atomic hydrogen diffuses readily into the metal and gets stored in the voids of
cavities where it may recombine to form molecular H2 (gas) according to

H+H H2
Accumulation of this gas in the voids of the metal develops a high pressure and
causes cracks and blisters. This is known as hydrogen embrittlement.

(b) Decarburization (at higher temperature)

At relatively higher temperature atomic hydrogen is formed by the thermal

dissociation of H2 gas accumulated in the voids

Heat
H2 H +H
When steel is exposed to this environment the atomic hydrogen readily reacts with
the carbon of the steel and forms methane gas
C +4C CH4
Accumulation of methane gas in the voids of the steel develops very high pressure
which causes cracking. This also results in decreasing of carbon content of the steel
and hence named as ‘Decarburization’ of steel.

III. Liquid metal corrosion

This corrosion occurs due to the flow of liquid metal at higher temperature. The corrosion
involves either the following

1. Dissolution of a solid metal by a liquid metal

2. Liquid metal may penetrate into the solid metal

WET (or) ELECTRO CHEMICAL CORROSION

Wet corrosion occurs under the following two important conditions:

1. Availability of anodic and cathodic regions on the surface of the metal

2. Availability of a conducting medium or an electrolyte.

When two dissimilar metals or alloys are in contact with each other in the presence of an
aqueous solution or moisture and when a metal is exposed to varying concentration of
oxygen or electrolyte, these conditions are satisfied. One part metal acts as the anode and
the other part as the cathode. This forms tiny galvanic cell on the surface of the metal and
favours the corrosion through electrochemical reactions.

Mechanism of wet corrosion

5
When one part of the alloy acts as anode and the other as cathode and corrosion occurs
and the following electrochemical reactions occur.

At anode: oxidation or dissolution of metal takes place at this electrode releasing electrons

M M2++ 2e-

At cathode: Reduction takes place using the electrons released at the anode. This depends
on the nature of the corrosive cathodic environment.

1. In acidic solutions

If the corrosive environment in acidic in nature, hydrogen gas is evolved according to

2H+ + 2e- H2
This type of attack takes place on the inner surface of pipelines where acidic industrial
effluents flow.

Acidic environment: Cathodic

H+Cl- H+Cl-

2H+ + 2e- H2

Fe Fe2+ + 2e-

Fe metal: Anodic

Fig. 2.3 Hydrogen evolution type corrosion

2. In neutral and basic solutions

If the corrosive environment is slightly alkaline or neutral then hydroxide ions form at
the cathodic part of the metal according to the oxygen reduction reaction

H2O +1/2O2 + 2e- 2OH-

The positively charged metal ions from the anodic region and the negatively charged
hydroxyl ions from cathodic region of the same metal diffuse towards each other through
the conducting medium and form the corrosion product called the RUST [Fe(OH)2 or Fe3O4.x
H2O] on the surface.

Hydrogen evolution type corrosion

Mechanism
When iron metal in contact with a non-oxidising acid like HCl, hydrogen evolution corrosion
occurs at the cathode. Oxidation takes place always at the anode. At anode, iron
undergoes dissolution to give Fe2+ ions with the simultaneous liberation of two electrons
(Oxidation)

6
 Fe Fe2+ + 2e-

At cathode: The liberated electrons at the anode flow to cathodic part and reduce the H+
ions to form hydrogen gas and the latter is evolved soon after the formation

2H+ + 2e- H2

(b) Oxygen absorption type corrosion

The surface of the iron metal is usually coated with a thin layer of iron oxide (FeO). However,
when the oxide film develops a crack or pore on the surface due to transporting the metal
or such reasons, the anodic and cathodic areas are created on the metal surface and
electrochemical oxidation and reduction reactions take place and corrosion occurs.

Atmosphere: Neutral

H2O H2O
OH- H2O
Fe(OH)3
Fe2+
Iron oxide

Iron metal (cathodic

Crack (anodic part)
Fe Fe2+ +2e-
Corrosion occurs

Fig. 2.4 Hydroxide ion formation corrosion

The corrosion reaction taking place at the anode and cathode can be written as given
below.

At anode: Iron dissolves to give Fe2+ ions with the simultaneous liberation of two electrons
(Oxidation)

Fe Fe2+ + 2e-

At cathode: The liberated electrons at the anode move to the surface of the metal and are
used by the dissolved oxygen to form OH- ions which then combine with Fe2+ to form the
corrosion product. ½ O2 + H2O + 2e- 2 OH-
The net reaction can be written as
O
Fe2+ + 2OH- Fe(OH)2 Fe(OH)3 Fe2O3.H2O

Table 2.1 Differences between chemical and electrochemical corrosion

7
 No Chemical corrosion Electrochemical corrosion
1 It takes place in dry condition
It takes place in the presence of
moisture or electrolyte
2 It involves direct chemical It is due to the formation of anodic
attack by environmental gases and cathodic areas
on the metal
3 Even a homogeneous metal Heterogeneous surface (or)
gets corroded bimetallic contact is necessary
4 Corrosion products gets Corrosion occurs at the anodic
accumulated on the place area and the products are
where corrosion occurs accumulated elsewhere
5 It is self controlled It is continuous
6 It follows adsorption It follows a electrochemical
mechanism reaction and degradation of metal
Formation of mil scale on the Example: rusting of iron in the moist
surface of the metal atmosphere

Types of electrochemical corrosion

1. Galvanic corrosion, 2. Differential aeration corrosion

1. Galvanic corrosion

When two dissimilar metals (one on the anodic region and the other on the cathodic
region of the e.m.f. series) are in contact with each other in presence of aqueous solution or
moisture, galvanic corrosion occurs. Ex: Zn-Fe and Zn-Cu systems.

Zn undergoes corrosion Zn undergoes corrosion

Electrolyte Electrolyte

(a) (b)

Zn, Anode Fe, cathode Fe, Anode Cu, cathode

EoZn = -0.76V EoFe = -0.44V EoZn = -0.44V EoCu = +0.34V

Fig. 2.5 Galvanic corrosion of (a) Zn-Fe and (b) Fe-Cu alloy systems

In this case the more active metal (with more negative electrode potential, Eozn = -0.76V)
acts as anode and the less active metal (with less negative electrode potential, EoFe = -
0.44V).

8
 Fig. 2.5 (a) represents a Zn-Fe alloy system in which zinc dissolves more readily than
iron hence zinc acts as anode and Fe as cathode thereby setting up a galvanic cell type
which facilitates the corrosion of zinc due to electrochemical reaction.

Fig. 2.5 (b) represents a Fe-Cu alloy system in which Fe dissolves more readily than
copper (EoCu = +0.34V) hence iron acts as anode and Cu as cathode thereby setting up a
galvanic cell type which facilitates the corrosion of iron due to electrochemical reaction.

Therefore it is understood that in an alloy system, the metal which is placed in the top
(with more reduction potential, more active) undergoes corrosion readily than the metal
which placed below to it. Hence, Zn undergoes corrosion readily than Fe and Fe undergoes
corrosion more readily than Cu (refer electrochemical series).

Examples for Galvanic corrosion

1. Corrosion of a steel screw in a brass marine hardware: This is due to the setup of a
galvanic cell type due to steel (Fe) acting as anode and brass (Cu = 90%, Zn=10%)
as cathode. Therefore the screw (Fe) undergoes corrosion because it is placed
above to copper in emf series and its reduction potential is - 0.44V.

2. Bolt and nut made of the same metal is preferred in practice because galvanic
corrosion can be avoided due to the homogeneity of the metals.

Prevention

This can be prevented by providing insulating materials between two metals so that
the contact between two meals can be avoided.

2. Differential aeration corrosion (or) concentration cell corrosion

This type of corrosion occurs when a metal is exposed varying concentration of

oxygen or any electrolyte on the surface of a 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 as shown in Fig. 2.6, the metal part
above the solution is more aerated and hence acts cathodic part and the metal part which
is inside the solution is less aerated and thus becomes anodic and undergoes oxidation and
thus corrosion.

At anode (less aerated) corrosion occurs and hence metal gets oxidised to metal ions

M M2+ + 2e-

At cathode (more oxygenated area) hydroxyl ions are produced

½ O2 + H2O + 2e- 2OH-

9
 Zn rod

Water line
More oxygenated part (cathodic
part)
1/2O2 + H2O + 2e- 2OH-

NaCl solution
Zn2+

Less oxygenated part (anodic

Zn 2+ part)
Zn Zn2+ +2e-
Undergoes corrosion
ZnCl2

Fig. 2.6 Differential aeration corrosion

Types of differential aeration corrosion (or) examples for it

1. Pitting (or) localised corrosion

2. Crevice corrosion
3. Pipeline corrosion
4. Corrosion on wire fence

1. Pitting corrosion

Formation of a hole or pit on the surface of a metal is called pitting corrosion. Pitting
corrosion is a localised attack, resulting in the formation of a hole around which the metal is
relatively not affected.

Water droplet

Metal surface

Cathodic
part
Pit
(anode)

Fig. 2.7 pitting corrosion

For example consider a small area covered by a drop of water, wet sand or a drop of NaCl
solution on the surface of a metal surface as shown in Fig. 2.7. The area covered d by the
drop of water acts as an anode due to less exposure to oxygen and suffers corrosion. The
uncovered area (freely exposed to air) acts as a cathode due to high oxygen
concentration. The rate of corrosion is more when the area of the cathode is larger ad the

10
area of the anode is small. Therefore more and more of materials is removed from the same
spot on the surface of the metal.

Hence, a small pit or hole is formed on the surface. If iron piece is considered as a metal
surface the reactions due to corrosion can be written as below,

At anode, the iron is oxidised to form Fe2+ ions

Fe Fe2+ + 2e-

At cathode, oxygen is converted to OH- ions and then combines with Fe2+ to form corrosion
product
½ O2 + H2O + 2e- 2OH-

Therefore the net reaction can be written as below

O
Fe2+ +2OH- Fe(OH)2 Fe(OH)3 Fe2O3

2) Crevice corrosion

Cathodic part
part

Wet crevice: anodic part

Fig. 2.8 Crevice corrosion

If a crevice between any two metallic objects or metallic and non-metallic materials is in
contact with liquid or moisture, the crevice becomes anodic part due to less exposure to
oxygen and undergoes corrosion. The exposed area acts as cathode.

3) Pipeline corrosion

Clay Sand

Less aerated More aerated

adnodic part cathodic part

Fig. 2.9 Pipeline corrosion

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When a pipeline passes under the ground it may pass through different types of sands. For
example if a pipeline passes through the sand and clay, the pipeline in the sand region is
more aerated and in the clay region is less aerated. Therefore, the pipeline in the clay region
acts as anodic part and suffers corrosion where as the sand region acts as cathodic part.
Hence a undedergorund water pipeline may undergo corrosion if it is made of steel.

4) Corrosion on wire fence

Anodic part

Cathodic

Fig. 2.10 corrosion on wire fence

The above figure shows a wire fence in which the areas where the wire crosses are less
aerated and acts as anode and suffers corrosion than the uncrossed areas which acts as
cathode.

FACTORS INFLEUNCING THE RATE OF CORROSION

The rate and extent of corrosion mainly depends on (a) nature of the metal and (b) nature
of the environment.

(A) NATURE OF THE METAL

1. Position in the emf series 2. Relative areas of anode and cathode

3. Purity of the metal 4. Over voltage or over potential

5. Nature of the surface oxide 6. Nature of the corrosion product

1. Position in the emf series

The extent of corrosion of a metal depends on the position of the metal in the emf
series. Metals above hydrogen in the emf series have more tendencies to undergo oxidation
and thus corrosion. The metals with lower reduction potentials undergo corrosion severely
than the metals with low reduction potentials. When two metals are in contact with each
other, the metal with low reduction potential suffers corrosion and the severity depends on
the difference in their position in emf series. Greater the difference between two metals in
their position greater will be the corrosion rate of anodic metal.

2. Relative areas of anode and cathode

12
 The rate of corrosion is directly proportional to the cathode area which means that if
the area of cathode is larger the rate of corrosion is high. When the cathodic area is large,
the demand for electrons will be high which results in increased dissolution of metals and
hence the corrosion.

3. Purity of the metal

% of purity of zinc 99.999 99.99 99.95

Rate of corrosion 1 2650 5000
The pure metal does not undergo any kind of corrosion but presence of impurities cause
corrosion due to the setting up of galvanic cell type cell. The impurity makes the pure metal
heterogenic and forms anodic and cathodic part hence, causes corrosion. More the
impurity, more will be the corrosion.

4. Overvoltage or Over potential

The over voltage of the metal in the corrosive environment is inversely proportional to the
rate of the corrosion.

For example, the hydrogen over voltage of zinc metal when is dipped in 1M H2SO4 is 0.7 V, at
this condition, the rate of corrosion is relatively low. But the over voltage of hydrogen can be
reduced to 0.33 V by the addition of small quantities of CuSO4 or H2SO4, which results in
increased corrosion rate.

5. Nature of the surface film

In aerated atmosphere, practically all metals get covered with an oxide film having a
thickness of few angstroms (1Å = 10-10 m). The thickness of the metal oxide depends on the
metal and the temperature of corrosion atmosphere. The metals such as Ca, Mg, Ba, Li etc
forms a oxide film whose specific volume is less than that of the volume of the metal, hence
the oxide film will be porous and oxygen can diffuse through that to bring about the further
corrosion. But, heavy metals like Al, Sn forms oxides whose specific volume is greater than
that of the volume of the metal, then the oxide layer will dense, protective and prevent the
further corrosion.

6. Nature of the corrosion product

Solubility of the corrosion product formed is an important factor in electrochemical

corrosion. If the corrosion product formed is soluble then the corrosion will proceed further.
On the other hand if the corrosion product is insoluble (most metal oxides), then the
corrosion will be suppressed.

(B) NATURE OF THE ENVIRONMENT

1. Temperature

The rate of corrosion is directly proportional to the temperature. The reason is that when the
temperature is increased, the rate of chemical reactions increases due to a high rate of
diffusion of free ions. Hence, the rate of corrosion increases with increases in temperature.

2. Humidity

13
The rate of corrosion will be more when the humidity of the environment is high. The moisture
in the atmosphere acts as a solvent for oxygen in the air to produce electrolyte which is
essential for setting up a galvanic corrosion cell.

3. Presence of corrosive gases

The acidic gases such as CO2, SO2, H2S and fumes of HCl, H2SO4 etc, produces electrolytes
and are acidic in nature. Moreover, these gases when dissolved in water, they increase the
PH of the medium and hence the high rate of corrosion.

4. Presence of suspended particles

Presence of suspended particles such as NaCl, (NH4)2SO4 along with moisture in the
atmosphere form an electrolyte and hence increases the electrochemical corrosion
reactions taking place in the atmosphere.

5. Effect of pH

The rate of corrosion depends mainly on the pH of the solution. If the pH is less than 7, then
the environment is acidic and more corrosion occurs. This can be explained with the help of
pourbaix diagram.
Passive (chemical inactive)
region

+1.6

+0.8
Electrode potential

Corrosion N (pH = 7, -0.4V)

0.0

-0.8
Corrosion
(volts)

-1.6

-2.0 Immune region

2 6 10 14
pH
Fig. 2.11 Pourbaix diagram

The pourbaix diagram for Fe in water is shown in the above figure. It shows different regions
of corrosion, passivity and immunity.

CORROSION CONTROL

CATHODIC PROTECTION METAODS

The important cathodic protection methods are 1) sacrificial anodic protection and 2)
Impressed current cathodic protection. The corroding metal is made to act as cathode to
prevent the corrosion in the cathodic protection method.

1. SACRIFICIAL ANODIC PROTECTION

14
 e- Flow

Zn

Underground Sacrificial

Fig. 2.16 Sacrificial anodic protection

In this method, the metallic structure to be protected is made as cathode and is connected
to a more anodic or more active metal than the metal or structure to be protected. So,
corrosion occurs only at the anodic metal which sacrifices itself in protecting the original
pipeline structure. There will be continuous flow electrons from anode to cathode as shown
in the above diagram. Since, the anodic metal is corroded completely protecting the
cathode, it is called sacrificial anodic protection method.

Applications of sacrificial anodic protection

1. This method is used for the protection of ships and boats. Sheets or blocks of Mg or Zn are
hung around the hull of the ship as shown in Fig. 2.17. The ship or boat is made of iron (Fe), so
Mg or Zn ribbons will act as anode and undergo corrosion protecting the ship.

Insulated copper

Sacrificial Zn or
Ship

Fig. 2.17 sacrificial anodic protection of a ship

2. It can be used for the protection of underground pipeline or cables from the corrosion
due to soil
3. Insertion of Mg sheets inside the domestic water boilers prevents the corrosion and rust
formation.
4. Calcium metal can be used to minimise the engine corrosion.

IMPRESSED CATHODIC CURRENT PROTECTION

15
It is another method of protecting the cathode from corrosion. In this method, impressed
current is applied in the opposite direction to the direction of the current due to corrosion to
nullify. By this act the corroding metal (cathode) is converted from anode to cathode.

- +
Cathod Anod
D

Back fill

Underground Graphite

Fig. 2.18 Impressed current cathodic protection

Consider an underground pipeline which is prone for corrosion due to soil. The corrosion can
be prevented by using an external battery (D.C source) which will act as current source to
nullify the current generated due to corrosion reactions. The negative terminal of the battery
can be connected to the metallic structure to be protected to make it as cathode
deliberately and positive terminal is connected to an inert anode. The inert anode can be
graphite or platinised titanium. The anode is usually buried in a “back fill” (which is a mixture
of gypsum, coke, sodium sulphate). The back fill provides good electrical contact to anode.

Uses

Underground structures like tanks, pipelines, transmission line towers, oil pipelines, ships, water
pipelines etc could be protected by this method.

Table 2.2 comparison of sacrificial anode and impressed current cathodic protection
methods

No Sacrificial anodic method Impressed current method

1 No external power supply External power supply is a must
needed
2 This requires periodical Anode is stable and does not
replacement of sacrificial anode deform but the investment is high
but the investment is low
3 Soil and microbiological corrosion Soil and microbiological corrosion
effects are not considered effect are taken in to
consideration
4 This is most economical when This is suitable for large structures
short term protection is required and long term protections
5 This is suitable when the current This can be practised even if
requirement and resistivity of the current required and the resistivity
electrolyte are relatively low are high

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CORROSION INHIBITORS

Corrosion inhibitor is a materials or substance which reduces the corrosion of a metal when it
is added to the corrosive environment.

The inhibitors are classified in to three types

1. Anodic inhibitors
2. Cathodic inhibitors
3. Vapour phase inhibitors

1. Anodic inhibitors

The substance that prevents the corrosion reaction occurring at the anode is called
anodic inhibitors. These substances form are insoluble compounds with the newly formed
metal ions due to corrosion reaction. The compound formed is adsorbed (adhered) on the
surface of the anode forming a protective film thereby reducing the rate of corrosion.

E.g. chromates (CrO4-), nitrates (NO3-), phosphates (PO4-), tungstates (WOx) other ions of
transition state elements with higher oxygen content (NiO2, Cr2O6, MnO4 etc).

Disadvantage: Though this type of control is effective in preventing the anodic corrosion, it
fails when the surface the metal is porous in nature as further corrosion can take place by
utilizing the pores of the surface.

2. Cathodic inhibitors

Substances that prevent the corrosion reaction occurring at the cathode is called
cathodic inhibitors. In an electrochemical corrosion, the cathodic reaction is of two types
depending up on the environment in which the cathode is placed.

E.g. Organic inhibitors: amines, mercaptans, heterocyclic nitrogen compounds, thioureas,

substituted urea and heavy metal soaps.

Inorganic inhibitors: Sodium sulphate (Na2SO3), hydrazine (N2H4)

(a) In an acidic solution

In an acidic solution, the cathodic reaction involves the evolution of hydrogen gas
2H+ + 2e- H2

Therefore the corrosion can be reduced in two ways

(i) The cathode reaction can be minimised by the slowing the speed of diffusion of
H+ ions towards the cathode. This can be done by adding organic inhibitors such
as amines or pyridines which get adsorbed on the cathodic metal surface and
prevent the diffusion of hydrogen ions towards the cathode.

(ii) Secondly, by increasing the overvoltage of hydrogen evolution. This can be done
by adding antimony and arsenic oxides which get deposited as well-adherent film
of ‘metallic arsenic or antimony’ on the surface of the cathode.

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(b) In neutral solution

In neutral solution the corrosion is due to the following reaction

H2O +1/2O2 + 2e- 2OH-

The corrosion can be minimised by two ways,

(i) Removing the oxygen from the neutral solution, thereby minimizing the formation
of OH- ions. This can be done by adding reducing agents like Na2SO3 and N2H4
known as ‘SCAVENGERS’. However, use of hydrazine is better than sodium sulphite
because the hydrazine does not leave with any chemical product which
increases the hardness of the medium as sodium sulphite does.

Na2SO3 + ½ O2 Na2SO4

NH2 – NH2 + 1/2O2 N2 + 2H2O

(ii) The OH- ions can also be removed by the addition of Mg, Zn or Ni salts also. These,
salts react with OH- ions to form insoluble hydroxides which are deposited on the
surface of the cathode forming impermeable self barrier coatings of oxides.

3. Vapour phase inhibitors (VPI)

Vapour phase inhibitors (volatile in nature) are organic compounds which readily vaporise to
form a protective layer on the metal surface. VPIs are used in the protection of storage
containers, packing materials and spare aircraft engines.

Eg. Cyclohexyl amine carbonate, Benzotriazole.

PROTECTIVE COATINGS
Protective coatings are used to protect the metal from corrosion. Protective coatings act as
a physical barrier between the base metal surface and the environment. However, they are
also used for decorative purposes. In addition to preventing corrosion and providing
decoration, they impart some special properties such as hardness, oxidation resistance,
electrical properties and thermal insulating properties to the coated surface.

Coatings may be classified as

Protective coatings

Inorganic Organic coatings

Metallic coatings Non-metallic coatings

Paints

Electroplating
18
 ORGANIC COATINGS
PAINTS

Paint is a mechanical dispersion of one or more finely divided pigments in a medium (thinner
and vehicle). When paint is applied on the metal surface, the thinner evaporates while the
vehicle undergoes slow oxidation forming a pigmented film.

Solvent

Vehicle (or)
medium
Fig. 2.19 Overview of
basic constituents of
Pigment

CONSTITUENTS OF AN OIL PAINT AND THEIR FUNCTION

1. Pigments 2. Vehicle or drying oil 3. Thinners or solvents

4. Extenders or fillers 5. Driers 6. Plasticisers 7. Anti-skinning agents

1. Pigments

Pigments are solid colour producing substances in the paint and their main functions
are

(i) Gives colour and opacity to the paint film

(ii) Provides strength to the film by forming adhesive film on the metal surface
(iii) Protects the paint film thereby the metal surface reflects the destructive and
harmful UV radiations.

Some examples:

White pigments White lead (PbCO3. Pb(OH)2)

Lithophone (75% BaSO4 +25%ZnS)
Black pigments Lamp black, carbon black

Red pigments Venetian red (Fe2O3 and CaSO4)

Indian red (Fe2O3)
Blue pigments Prussian blue [Fe4(FeCN)6]3
Green pigments Cr2O3 (chromium oxide)

2. Vehicle (or) drying oil

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 This is a non-volatile portion of a paint which is film forming constituent. These are high
molecular weight fat acids extracted from vegetable and animal oils.

The functions of this constituent are

1. They are responsible for the formation of film by the oxidation followed by
polymerisation of the drying oil
2. They hold the pigment particles together on the metal surface (acts as binder
between pigment and metal surface)
3. They impart water repelling nature, toughness and durability to the film.

Examples: Linseed oil (form Flax seed or from any plant of genus Linum), dehydrated castor
oil.

3. Thinners (or) solvents

This is a volatile (easily vapourisable) portion of the paint. It easily evaporates

immediately after the application of the paint.

Its functions are as follows.

1. It reduces the viscosity of the paint and prevents the solidification of the so that the
paint can be applied easily on the metal surface
2. It dissolves the oil, pigments etc in a paint and makes a homogeneous mixture
3. It increases the elasticity of the paint film
4. It increases the penetrating power of the vehicle on the metal surface

4. Extenders (or) fillers

These are white or colourless pigments present in the paint. The functions include the
following

1. It prevents the settling of the pigments in paints

2. It modifies the shades of the pigments
3. prevents shrinkage and cracking of the paint film

Examples: talc, gypsum, china clay.

5. Driers

These are the substances which increase the speed of drying process by the oxidation
of the pigments.

The functions are

1. They act as oxygen carriers or catalysts thereby supplying oxygen to the organic
pigments so that the process of oxidation and polymerisation will be fast and hence
drying.

Example: Metallic soaps, linoleates and resonates of Co, Mn and Pb.

6. Plasticizers

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 Plasticizers are chemicals added to the paint to provide elasticity to the paint film and
to prevent cracking of the film.

Examples: Triphenyl phosphate, tricresyl phosphate, dibutyl phthalate.

7. Anti-skinning agents

These are chemicals added to the paint to prevent gelling and skinning of the paint.

Examples: Polyhydroxy phenol.

METALLIC COATINGS
Deposition of metallic thin films can be done by

I. Physical vapour deposition (PVD)

II. Chemical vapour deposition (CVD)

III. Electro deposition (or) electroplating

I. ELECTROPLATING

Electroplating is the well known and simple technique used for the large scale production or
deposition of metallic thin films over different substrates.

Aim/Objectives of electroplating

1. On metal surfaces
(i) To increase the corrosion resistance
(ii) To improve the hardness and physical appreance
(iii) To increase the decorative and commercial value of an article
(iv) To increase the resistance to chemical attack
(v) To improve the properties (electrical, mechanical etc) of the article

2. On Non-metals
(i) To enhance the strength of the materials (e.g. coated plastic)
(ii) To decorate and persevere the surfaces like plastics, wood, glass etc
(iii) For making surface conductivity materials using non-metals

Principle
Electroplating is a process in which a metallic film (source metal, anode) is deposited
on the base metal (target metal, cathode) by passing electricity through an electrolyte
solution containing the soluble salt of the film forming metal.

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 DC battery
Theory and process

Au
(Anode)

Cu object
Au3 (cathode)
Au3+
+

AuCl3
Au deposited
surface

Figure 2.20 Electroplating of gold over copper substrate

Electro deposition results in the formation of a coating of uniform composition. It is

driven by a voltage applied between the anode, consisting of the metal used for plating,
and the cathode, which is the object to be plated. The molten salt medium, in which the
anode and cathode are immersed, consists of a soluble form of the metal used for plating
(aq. AuCl3) dissolved in a molten salt solvent, such as an alkali metal halide, which does not
participate in the plating process.

The copper object to be plated is treated with dil. HCl or dil.H2SO4 for surface cleaning
which removes any particulates on the surface of the metal to be coated. The same can be
done using ultrasonic water bath. The cleaned object is then made as cathode of an
electrolytic cell and gold foil is used as anode (metal used for plating). Gold chloride (AuCl3)
solution is used as electrolyte in which the anode and cathode are immersed. When the
current is passed between these two electrodes, gold particles dissolves and gets deposited
uniformly on the surface of the copper object. When the anode is made of gold foil the
concentration is electrolyte solution is compensated by the continuous reactions of anions
with anode.

Chemical reactions

Gold chloride, AuCl3 ionises as Au3+ ions in the electrolyte solution

AuCl3 Au3+ + 3Cl-

At cathode: When current is passed, Au3+ ions move towards the cathode and deposited
(get reduced) as metallic (Au) film

Au3+ + 3e- Au

At anode: The ionised chloride ions migrate towards the gold anode and reacts with the
gold to form AuCl3 so that the concentration of the electrolyte is maintained which helps in
continuous deposition of metallic film
Au3+ + 3Cl- AuCl3

In order to get good adherent metallic film, certain additives are added to the electrolyte
bath. Some brightening agents are also added. Favourable condition to get a good
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electrodeposited film may vary with the nature of the metallic film; hence process
parameters such as electrolyte concentration, temperature of the deposition, applied
current density, have to be optimised prior to the deposition. For a good electro deposit,
optimum temperature of 60oC and current density of 1-10mA/cm2 and low metal ions
concentration may be required.

Uses

1. The gold deposit is used for electrical and electronic applications

2. It is used for high quality decorations and high oxidation resistance coatings
3. For making jewellery thin coatings of 0.05 – 1.0 microns are needed.

II. ELECTROLESS PLATING

Electroless plating is a technique of depositing noble metal from its salt solution on a
catalytically active surface of the metal to be protected by using suitable reducing agents
without using electrical energy. In short, the metal ions of the electrolyte are reduced by the
reducing agents and deposited as a metallic coating over the substrate chosen for plating.

Source
Uncoated
solution
stainless steel
Ni2+
Ni Coated stainless
Ni2+ +
steel substrate

NaH2P Plating

Reducing agent
(sodium hypo

Fig 2.21 Electroless plating of nickel

Electroless nickel plating involves following steps.

Step I: Pre-treatment and activation of substrate surface

The surface of the object to be coated is cleaned to remove any contaminants by

treating it with organic solvents followed by acid solution in a clean environment, so that
impurity incorporation on to the surface can be avoided after surface cleaning.

For the deposition of good adherent film, a seed layer of usually few manometers
(nm) is deposited prior to the actual deposition of metallic film.

1. Metals and alloys like Al, Cu, Fe and brass etc can be coated directly without
activation after cleaning of their surfaces
2. Stainless steel (SS) substrates can be cleaned and activated by dipping in to the
solution of 50% dil. H2SO4
3. The surface of Mg alloy is activated after cleaning by coating a thin film of Zn and Cu
over the surface

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 4. Non-metallic substrates such as plastic, glass etc are cleaned by dipping in SnCl2+HCl
solution for cleaning the surface followed by the deposition of Pd seed layer by
dipping in PdCl2 solution. On drying a thin layer of Pd is formed on the surface.

Step II: Materials or chemical for the deposition of Ni thin film (preparing the plating bath)

As shown in the above figure the required chemicals for the Electroless plating of nickel are

1. Source solution –Nickel chloride (NiCl2), 20g

2. Reducing agent – sodium hypophosphate (NaH2PO2), 20g – used for reducing metal
ions
3. Complexion agent – sodium succinate, 25g – improves the quality of the film
4. Buffer solution – sodium acetate, 10g – to control the pH of the medium
5. Optimum pH of 4.5 should be maintained and
6. Optimum temperature of 93oC has to be maintained for the deposition

Step III: Electroless plating process

The pre-treated object is immersed in the plating bath for a required period of time.
The coating time and thickness depends on the nature of the application. During the
process of coating the following reactions occurs and nickel ions gets reduced to metallic
nickel film

At anode: Oxidation
Na+H2PO2- + H2O H2PO3- + 2H+
At cathode: Reduction of Ni2+ to metallic Ni
Ni2+ +2e- Ni

Over all reaction Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2H+

Applications:

1. Electroless Ni plating is extensively used in electronic application

2. It is used in domestic as well as automotive fields such as coating jewellery, top of
perfume bottles etc.,
3. Electroless Ni plated polymers are used in decorative and functional works
4. Electroless nickel and copper coated body is used in digital as well as electronic
instruments

Advantages of Electroless plating over electroplating

1. No electricity is required for the coating

2. It can be carried out on plastics, glass and semiconductor for electronic applications
3. Complicated objects can also be plated
4. Electroless plating provides better mechanical, chemical and electrical properties of
the object coated.

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Table2.1 Comparison between electro plating and Electroless plating

No Electroplating Electroless plating

1 It is carried out by passing
It is carried out by the
electricity from an external
autocatalytic redox
source reaction
2 Oxidation occurs Both
at occurs at the
anode and metal gets catalytically activated
reduced and deposited at surface of the object to
cathode be coated
3 Anode undergoes
Reducing agent supplies
reduction and supplies electron for reduction of
electron for reduction metal
4 It is not satisfactory for
It is satisfactory for all
objects with irregular
objects with complex
shapes geometries
5 The object to be coated is
It can be carried out on
a conducting material conducting,
semiconducting or plastic
objects
6 The thickness of the Thickness of the plating is
coating is usually 1-100 1-100micrometer
micrometer

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