Chapter II

CORROSION
and its CONTROL
 CORROSION AND ITS
CONTROL

DEFINITION
Corrosion is defined as the gradual destruction
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.

3
 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, and 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-

Oxygen changes to ionic form (O2-) due to the transfer

of electron from metal, which occurs at the oxide
film / environment interface.
O2 + 2e- O2-

Oxide ions reacts with the metal ion to form the

metal- oxide film.

M + O2 M2+ +O2- MO (Metal-oxide film)

6
 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 has fine grains

structure it behaves as a protective
coating by strong adhesion on the metal
surface 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 dissociate in to the metal and oxygen.
Metal oxide Metal + Oxygen

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

Exposed surface
Unstable Metal Oxide

+ O2 Metal oxide
Metal Metal
Metal decomposes Metal +O2
Of air

Unstable metal oxide

8
(iii) VOLATILE OXIDE LAYER
The oxide layer volatilizes as soon as it is formed, leaving
the metal surface for further corrosion.

2Mo +3O2 2MoO3

[Sn +2Cl2 SnCl4 (Another example for volatile
corrosion) keep it in your mind this is not oxide coating]

Example: Molybdenum oxide is volatile.

Exposed surface Fresh surface exposed

Volatile Metal oxide
for further attack

+ O2 Metal oxide
Metal
Metal volatalizes Metal
Of air

Volatile metal oxide

(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. Eg. Fe
Exposed surface Porous Metal oxide

Further Attack
through pores
& cracks continues

10
 Pilling-Bedworth ratio (P-B ratio)
The P-B ratio, in corrosion of metals, is the ratio of the
volume of a metal oxide to the volume of the metal
exposed (from which the oxide is created).
The P-B ratio is defined as:

RPB is the Pilling-Bedworth ratio

RPB < 1 : the oxide layer is too thin, likely broken
M - the atomic or molecular mass and provides no protective effect (ex. Mg)

n - number of atoms of metal per RPB > 2 : the oxide layer chips off provides no
one molecule of the oxide protective effect (ex. Fe)

density 1 < RPB < 2 : the oxide coating is passivating and

provides a protecting effect against further surface
11

V the molar volume oxidation (ex. Al, Ti and Cr containing steels)

(PILLING-BEDWORTH RULE)

According to PillingBedworth rule,

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

volume of the metal, the oxide layer is too thin and it is 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.
12
 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 is prevented by
AgCl film.
(2) If the film is porous or non-protective, the surface of the
whole metal is gradually destroyed.
Eg. Dry Cl2 gas attack on Sn formation of volatile SnCl 4
fresh surface is exposed for further attack
13
 CORROSION BY HYDROGEN

(a) HYDROGEN EMBRITTLEMENT:

Contact of metal with H2S results in the generation of atomic

hydrogen
E.g. Fe + H2S FeS + H2
In petroleum industry steel is attacked by H 2S at high
temperature and forms FeS scale.
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.
18
(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.

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 20
reduced to H2.
21
 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 on surface corrosion
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 O2, OH- ions are formed.

At anode: Iron (Fe) undergoes dissolution to Fe2+ with the

liberation of electrons.

At cathode: The liberated electrons follow from anode to

cathode, where dissolved O is
O2 + H2O + 2e- 2OH
2 consumed
- to form OH -

ions.
Fe2+ + 2OH- Fe(OH)2 22
 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 (Cell)
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 23
iron surface atmosphere
 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).

Control measures:
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
O2 +H2O + 2e- 2 OH- 27
Examples for differential aeration
corrosion

Pitting or localized corrosion

Crevice corrosion
Soil corrosion
Fencing Corrosion
Waterline Corrosion

28
 (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. (1/2 O2 +H2O +2e- 2OH-)

Net reaction is
Fe2+ +2OH- Fe(OH)2 Fe(OH)3
30
This type of corrosion is called pitting.
 (b) Crevice corrosion
Crevice corrosion occurs at narrow openings or spaces between two
metal surfaces or between metals and nonmetal surfaces.
A concentration cell forms with the crevice being depleted of oxygen.
This differential aeration between the crevice and the external
surface gives the crevice an anodic character. This can contribute to
a highly corrosive condition in the crevice.
This is due to less oxygen with crevice area.
The exposed areas act as the cathode.

Some examples of crevices are listed below:

Flanges
Deposits
Washers
Rolled tube ends
Threaded joints
O-rings
Gaskets
Lap joints
Sediment 31
 (c) PIPELINE CORROSION
Differential aeration corrosion may also occur in
different parts of pipeline.
Buried pipelines from one type of soil to another,
example from clay (less aerated) to sand (more
aerated) may get corroded due to differential
aeration.

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

(burnt coal) or sand undergo corrosion. Since the
pipeline under cinders is more aerated, it gets
corroded easily.

32
 (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.

33
 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 galvanic series
The extent of corrosion depends upon the position
of the metal in the galvanic 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
galvanic series becomes anodic and suffers
corrosion.
Further, the rate and severity of corrosion depends
upon the difference in their positions in the
galvanic series.
Greater the difference, faster is the corrosion of
anodic metal.
Galvanic series

36
(b) Hydrogen overvoltage:
Hydrogen overvoltage is defined as the potential that
exists between a hydrogen electrode and an electrode of
Metal or alloy in the same electrolyte, at which H + ion
reduced to form H2 gas.

Metal or alloy with higher H2 overvoltage will corrode

lesser than the metal or alloy having lower H2 overvoltage.

For example if you keep Zn in 1N H 2SO4 will undergo

corrosion very slowly. (H2 Over voltage of Zn = 0.70 V)

But if you add few drops of CuSO4 soln. to the 1N H2 SO4

corrosion will be faster. This is due to the formation of
minute CuSO4 film formation on the Zn, which acts as a
cathodic part and reduces the H2 Overvoltage to 0.33 V.
37
 (c) 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.

CorrosionAnodic (Cathodic part) / (Anodic part)

Ex. A small steel pipe fitted in a copper tank

Steel will undergo corrosion (oxidation) at a faster rate, due

to the availability of large cathodic area (Cu ) for reduction of
38
released e from steel (Fe anode).
-
(d) Purity of the metal
Impurities in a metal create
heterogeneity. Thus it form a small
galvanic cell at the exposed surface.
Anodic part will get corroded.

Ex. Zn metal with impurities of Pb

and Fe enhances the corrosion of Zn
due to the formation of local
electrochemical set up.

Higher the percentage of impurity,

faster is the rate of corrosion of the
anodic metal. Go to 36
(e) Physical state of the metal

Metal components subjected to unevenly

distributed, stress on the metal will be created
due to the grain size and crystal orientations on
the surface.
The regions of high residual surface will tend to
be anodic with respect to the stress free surface.
This results in stress corrosion.
An uneven surface also get corrodes due to the
presence of crests and troughs.
Smaller the grain size greater will be its
solubility and greater will be its corrosion
40
 (f) Nature of the oxide film
In aerated atmosphere, mostly all metal forms oxide film
coating. The ratio between the volumes of metal oxide and
the metal is known as specific volume ratio.
Greater the specific volume lesser the oxidation corrosion,
if it is protective coating.
For example, the specific volume ratio of Ni, Cr, W are 1.6,
2.0 and 3.6 respectively.
of tungsten is least even at
The rate of oxidation
elevated temperature.
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 non-protective,
non-protective
through which oxygen can attack and facilitates further
corrosion.

41
(g) Stability 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.
In the electrochemical corrosion, if the
corrosion product is soluble in the
corroding medium, then corrosion proceeds
at a faster rate.
For example: Pb forms insoluble PbSO4 when
it contact with H2SO4, the PbSO4 is protect
42

the Pb metal for further corrosion.

(h) Volatility of the Corrosion Product

If the corrosion product is volatile, it volatilizes as soon

as it is formed, thereby leaving the underlying metal surface
exposed for further attack.
This causes rapid and continuous corrosion, leading to
Excessive corrosion.
For example
(i) Molebdenum oxide formation on Mo
2Mo + 3O2 2MoO3

(ii) Tin tetrachloride or stannic chloride formation

Sn + 2Cl2 SnCl4 (Mp of SnCl4 = - 33 C)

Information to you:
Stannic chloride was used as a chemical weapon in World War I, 43

as it formed an irritating (but non-deadly) dense smoke on contact with air

 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 (stable) metal may become
active at a higher temperature.
44
(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.

45
(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.

46
 (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.
47
(E) Conductance of the corroding 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.

48
 CORROSION CONTROL
The rate of corrosion can be controlled by either
modifying the metal or the environment.

1. Proper Designing (Refer Eng. Chem. By Jain & Jain)

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
4) Avoid differential aeration

Galvanic corrosion can be prevented by the following

methods,
a) Use an electrical insulators
b) Introduce an easily exchangeable corroding places
c) Avoid protruding parts.
 2. Cathodic Protection
The principle involved in cathodic
protection is to force the metal to
behave like a cathode. Hence, it is
protected.
Since, there will not be any anodic
area on the metal, corrosion does not
occur.
There are two types of cathodic protection.
1. Sacrificial anodic protection method.
2. Impressed current cathodic protection method.
 SACRIFICIAL ANODIC PROTECTION METHOD
OR
CATHODIC PROTECTION USING SACRIFICIAL ANODE

In this method, the metallic structure, which is to

be protected is made as 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, they are
called sacrificial anodes.
53
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. graphite or
platinized titanium
The anode is surrounded by
backfill (containing mixture of Protected Metal
gypsum, coke, sodium sulphate) to
improve the electrical contact
between the anode and the
surrounding soil.
56
 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 effects Soil corrosion effects
are not taken in to are taken in to
account. account.

This is most This method is well

economical method suited for large
especially when structures and long
short-term protection term operations.
is 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.
In a neutral solution, the cathodic reaction is,
H2O + 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 N4H4, Na2S, Na2SO3 or by deaeration.

Salts of Zn, Mg, Ni are employed as they form

insoluble metallic hydroxide which forms
impermeable self barriers.
61
 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
neutralizers (like NH3, NaOH, lime etc).
 CORROSION INHIBITORS

DEFINITION
A corrosion inhibitors is a substance which when
added 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, nitrite, nitrate or
transition metals with high oxygen content,
inhibit the anodic corrosion reaction by
forming sparingly soluble compound with a
newly produced metal ion (at the anode).

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
and this can produce severe corrosion.
 CATHODIC INHIBITORS
By slow down the cathodic reaction

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 to the cathode or by increasing
the H2 over voltage.

This can be done by adding organic inhibitors like amines,

pyridine, azoles azoles, mercaptans, etc.

They absorb over the cathodic metal surface and act as a

protective layer.

As, Sb inhibitors form a adherent film on the cathodic area and

it increases the hydrogen over voltage.
Eg As + 3H+ + 3e- AsH3 (acidic medium)
As + 3H2O +3e- AsH3 + 3OH- (neutral medium)
 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.
69
 Sample Preparation (contd..)
Alkali Cleaning To remove old paints that are soluble in
alkaline medium using chemicals like NaOH, Na 3PO4 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.

Piranha (H2SO4 + H2O2)

70
 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.
Crack Eozn = -0.76V Zn film

Steel (or) Fe EoFe = -0.44V

71
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.
Crac
k
Sn
film
EoSn =
Steel (or) Fe EoFe = -0.14V
-0.44V

72
Methods of application of thick metallic coating

Galvanizin
Hot dipping g
Tinning
Metal cladding
Electroplating Cu, Cr, Ni, Au, Ag
Cementation
Vacuum metalizing
Metal spraying

73
 1. 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 liquid of the metal to be coated.

Examples: Galvanizing and Tinning

74
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 (60-900C) 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

75
Galvanization process

NH4Cl flux to
avoid ZnO
formation

Hot air Galvanized

Steel sheet Steel
Pair of Hot Sheet
rollers

Annealing
chamber
250oC

Hot air

Washing Molten Zn at Excess Zn

Dil. H2SO4 at Collector
bath 425 430oC
60 90oC

76
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 ZnCl 2.

Then it is allowed to pass through molten Sn.

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.

77
Process of Tinning

Palm oil
Molten ZnCl2 avoids SnO2 Tinned
formation Steel
Sheet
Steel sheet

Hot rollers

Dil. H2SO4 at
60 90oC
Palm oil
Molten Sn
Acid Pickling

78
2. Metal Cladding

It is the process of sandwiching 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.

Duralumin sandwiched between Al sheets and hot rolled

to produce Alkad composite which is free from stress
79

corrosion
 3. 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 metal to be coated.

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. 80
 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. 81
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 jewelry,
refrigerator, electric iron etc.
82
 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 (Object or substrate) to be coated
Additive: Boric acid or gelatin
Ionization reaction of electrolyte:
CuSO4 Cu2+ + SO42- ; H2SO4 2H+ + SO42-

On passing current:
Cu + SO42- CuSO4 + 2e- (at anode)
Cu2+ + 2e- Cu (at cathode)
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 83
to 1.5
ampere/dm2.
 Electroplating
process
1. CuSO4 Cu2+ + SO42- (At cathode, reduction process)

2. Cu + SO42- CuSO4 + 2e- (At anode, oxidation of

metal )

DC battery

Cu
(Anode) Steel object
+ ve Cu2+ (cathode) (-ve)
Cu2+

Cu2+ SO42-
Cu
deposited

surface

84
 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 area of the base metal)
should be low for uniform controlled deposition
Additives: Ensure strong adherence and mirror smooth
coating.
pH of the electrolyte.

85
 Thin-Film Coatings

PVD Coating (Physical Vapor Deposition)

CVD Coating (Chemical Vapor Deposition)

86
Deposition techniques

87
 ION IMPLANTATION
Ion implantation in which ions of a
material can be implanted into
another solid.

After implantation the solid may

have change in physical, chemical
or electrical properties of the
solid.

Ion implantation is used in

semiconductor device fabrication
and in metal finishing, as well as
various applications in materials
science research.
 Ion implantation equipment typically consists of
an ion source, an accelerator, and a target
chamber.

The ions are produced from the ion source by

applying high electrical potential.

The ions thus produced are accelerated

electrostatically by applying same charge of the
ions and/or magnetic field.

Hence the ions will have high energy.

These high energy ions are made to strike the

surface (substrate), where we are going to coat
this metal.

Each ion is typically a single atom or molecule,

89
and thus the actual amount of material implanted
90
Block Diagram

Ion implantation equipment typically consists of an

1. Ion source, where ions of the desired element are produced

2. An accelerator, where the ions are electrostatically accelerated to a high
energy
3. And a target chamber, where the ions impinge on a target, which is the
material to be implanted.

Accelerat
or

Ion source
Energies of 1 10 keV is
used to penetrate only few substrat
nanometers of the surface
e

Target 91

chambe
Deposition by Physical Vapour Deposition (PVD)
H2 = 50 sccm
N2 = 15 sccm
Sccm = standard cubic centimeter per minute
Standard condition:Temp : 0 C, Pressure :1.013 bar / 1 atm / 14.69 psi
PVD Chamber
Substrate
Ni film

Heater

Suction
N2
Ni Source valve
(or) 2000oC
H2
To vacuum
pump 92
02/23/17 19:48 92
Nanotechnology
 Electron Beam Physical Vapor
Deposition or EBPVD
Tungsten filament is heated electrically.

Electrons are ejected from the W filament .

The target anode (ie. metal which we are going to coat

on the substrate) is bombarded with an electron beam
under high vacuum.

The electron beam causes atoms from the target to

transform into the gaseous phase.

These atoms then precipitate into solid form, coating

everything in the vacuum chamber (within line of sight)
with a thin layer of the anode material on the substrate.
93
Electron beam physical vapor deposition

94
 In an EBPVD system, the deposition chamber is evacuated to a
pressure of 10-4 Torr.
The material to be evaporated is in the form of ingots.
There are as many as six electron guns, each having a power from tens
to hundreds of kW.
Electron beams can be generated by thermionic emission, field electron
emission or the anodic arc method.
The generated electron beam is accelerated to a high kinetic energy
and focused towards the ingot.
When the accelerating voltage is between 20 kV 25 kV and the beam
current is a few amperes, 85% of the kinetic energy of the electrons is
converted into thermal energy as the beam bombards the surface of
the ingot.
The surface temperature of the ingot increases resulting in the
formation of a liquid melt. Although some of incident electron energy
is lost in the excitation of X-rays and secondary emission, the liquid
ingot material evaporates under vacuum.
The ingot itself is enclosed in a copper crucible, which is cooled by
water circulation. The level of molten liquid pool on the surface of the
ingot is kept constant by vertical displacement of the ingot. The
number of ingot feeders depends upon the material to be deposited. 95
The evaporation rate may be of the order of 10 g/cm sec.
-2 2
 Chemical Vapour deposition
process
CVD involves the formation of a solid film on a surface of a heated substrate by
CVD involves the formation of a solid film on a surface of a heated substrate by
means of a chemical reaction in a gas (or in the vapour) phase.

The complex molecule in the vapour state impinges on the hot substrate,
decomposes and forms a thin film. These reactions are promoted by
resistance, RF or infrared radiation heating.
Example: Monds Process

150C
Ni(CO)4 Ni + 4CO

Requirements for a CVD process

1. Vacumised chamber (10-3 mbar) connected to a rotary pump
2. Complex chamber with heating facility
3. Vapour transport SS tubes ( quarter inch)
4. Substrate holder inside the chamber withy heater (flat heater
900oC)
96
5. High Temperature valve to control the flow rate of complex
vapour
 CVD
Process
Step 1: The vapour source of the film-forming material may be
a solid, liquid, vapour or gas. Solid materials, having sufficient
vapour pressures, need to be vapourised to transport them at
moderate temperature to the deposition zone where the
substrate is placed, and this is normally achieved by heating.

Step 2: Another issue is the uniformity of arrival rate of vapour

sources by transport to the hot substrates. This uniformity in
transporting the vapour source varies with the transport
medium used to transport the source to the destination (i.e.
either by high vacuum or fluid (gaseous fluid).

Step 3: Deposition is the third step in a process of developing

thin-films, in which the actual growth of film over the surface
occurs.

Step 4: Once the deposition is over, the next step is the analysis
of coated thin-films by various techniques. Analysis of thin-films
can be thought of as the final stage process of monitoring but it
is important in all steps of thin-film deposition. 97
Deposition by Chemical Vapour Deposition
(CVD)
H2 = 50 sccm
N2 = 15 sccm

Sccm = standard cubic centimeter per minute

Standard condition:Temp : 0 C, Pressure :1.013 bar / 1 atm / 14.69 psi
CVD Chamber

Ni film

Substrate
Pre
Vap Heater

Suction
N2
Solid valve
comple (or)
x
H2
source
400oC To vacuum
pump 98
02/23/17 19:48 Nanotechnology 98
CVD Mechanism

99
Preliminary step
-cleaning Solid, liquid, Stages during
Source
vapour, gas thin-film process
Supply rate

vacuum, fluid,
Transport
plasma
Uniformity
Substrate condition
Deposition Reactivity of source material
Energy input

Annealing

Surface and composition

Structure Composition
Analysis properties

Process modification
100
 Process of making thin film and further..

H 3C H CH3
C N O C Characterisation
HC Ni CH CVD
C O N C
H 3C H CH3
As deposited
film on Si
Ni complex substrate SEM Image Ni film at 500oC

Micro patterned chip by lithography

101