CORROSION

and its CONTROL

Dr. K. Rajendra Kumar

Department of Chemistry
VIT University Chennai campus
Chennai

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DEFINITION
Corrosion is defined as the gradual
destruction or deterioration of
metals or alloys by the chemical or
electrochemical reaction with its
environment.
 Slow
Surface phenomenon
Amount of Iron wasted is of total
production
A huge loss of 2 to 25 billion dollars per year

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 Metals
Ores

Copper ores Stable

Bauxite
Unstable

Hematite
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Iron Pillar, Delhi

Kelpies, Scotland

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patina The patina slows corrosion because it
resists the electron flow in a corrosion cell

Multi-colored Cu2O films

deposited on copper.

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Brown Nails
Iron

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 In pipes or tanks due to the corrosive action
of either water or soil.

Water should be neither corrosive nor scale forming

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 The fourth most abundant element in the
earth's crust

Similar to aluminium Passivity

TiO2 impervious to air/contaminants

In a chloride-rich environment, the passive film will be

severely degraded corrosion may take place.
http://www.azom.com/article.aspx?ArticleID=1225

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The tarnishing of silver requires an
atmosphere containing hydrogen sulfide,
oxygen and water vapor.

A electrochemical mechanism is proposed

for the tarnishing of silver.

Corrosion (2001), 57, 12, 1066-1074.

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 The most electrically conductive of all
metals.
Convey even a tiny electrical current in
temperatures varying from -55 to +200
centigrade

Gold Tarnishing?

Golden Buddha Statue,

Bangok, Thailand

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 Possible causes include:
Perspiration (everyone's body chemistry is different)
Perfume, hair or deodorant sprays,
Tarnishing during storage (storage boxes may contain
organic sulfur compounds),
Leaching of acid/ cleaning solutions from surface
microporosity from cast jewelry; this causes corrosion locally
(such porosity may even trap perspiration during wear,
causing local corrosion)
Preparation of vegetables such as onions and spices (many
foodstuffs contain sulfur compounds and others are also
acidic).

www.jewellerycatalogue.co.uk/gold/allergy.php
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 Iridium

0.001 ppm in crustal rock

Spinneret

Willamette Meteorite
-4.7 ppm Iridium

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1. Dry indoor location and/or outdoor
location in a rural environments.
2. Outdoor location in a heavy industrial
environment.
3. Wet location with minimal chemical
exposure.
4. Wet location with moderate chemical
exposure.
5. Wet location with salts, acids, and
alkalines exposures.

1. None. Failure will not affect safety or

operations.
2. Increased maintenance costs will be
incurred.
3. Production/operations capacity will be
impaired.
4. Production/operations will stop.
5. Operations/Human Safety at risk due to
catastrophic failure of application.
http://www.corrosioncollege.com/corrosion-matrix.cfm 12/4/2017 18
 At normal temperatures iron will not corrode appreciably in
the absence of moisture.

The presence of oxygen is also essential for corrosion to take

place in ordinary water. Oxygen alone will cause considerable
corrosion in acid, neutral, or slightly alkaline water.

In natural waters, the rate of corrosion is almost directly

proportional to oxygen concentration, if other factors do not
change. Oxygen also accelerates the corrosion of iron in non-
oxidizing acid solutions of moderate strength.
.

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 Corrosion in acid solutions is much more rapid than in neutral solutions, and the latter is more rapid
than in alkaline solutions.
Hydrogen gas is usually evolved from the surface of the metal during corrosion in acid solutions.
The products of corrosion consist, mainly, of black or green ferrous hydroxide next to the metal, and
reddish-brown ferric hydroxide (rust) which forms the outer layer, with graded mixtures of the two
in between.

In natural water, the precipitated rust usually carries down some compounds
containing lime,, magnesia, and silica, together with other insoluble material from
the water. These substances have considerable influence on the structure and
density of the rust coating on the metal surface.' A loose, nonadherent coating
under ordinary conditions may accelerate locally the rate of corrosion; a uniformly
dense and adherent coating may cut down this rate very considerably.
Surface films, sometimes invisible, often play an important part in controlling the
rate and distribution of corrosion. These films have been made visible by
separation from some metals and have been shown to raise the potential of these
metals making them more resistant in certain environments. In fact the superior
resistance of metals like chromium and aluminum, for example, is undoubtedly
due largely to the formation of such films.

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 When iron corrodes in the atmosphere the amount of
ferrous rust produced is small, but when formed under
water the corrosion products often contain a large
proportion of ferrous iron.
Corrosion at normal temperature increases with
increase of concentration in dilute solutions of many
neutral salts, particularly chlorides, but decreases again
in more concentrated solutions, other things being
equal.

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Giovanni Aldini, Italy

Galvanism

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Svante Arrhenius,Sweden

conductivities of electrolytes

Jns Jacob Berzelius, Sweden

chemical formula notation,

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 CLASSIFICATION OF CORROSION
Based on the environment, corrosion is classified in to
1. Dry or Chemical corrosion
2. Wet or Electrochemical corrosion.

Dry or Chemical corrosion:

Dry corrosion is due to the attack of metal surfaces by
the atmospheric gases such as oxygen, hydrogen
sulphide, sulphur dioxide, nitrogen, inorganic liquids
etc.

There are three main types of dry corrosion;

1. Oxidation corrosion (or) corrosion by oxygen

2. Corrosion by hydrogen.
3. Liquid metal corrosion.

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 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 (except Ag,
Au and Pt) are oxidized.

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 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-

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 Dry Corrosion contd.

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)

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Oxidation

Oxide is the more stable than the metal (for most metals)
Oxidation rate becomes significant usually only at high temperatures
The nature of the oxide determines the rate of oxidation

Free energy of formation for some metal oxides at 25oC (KJ/mole)

Al2O3 Cr2O3 Ti2O Fe2O3 MgO NiO Cu2O Ag2O Au2O3
1576 1045 853 740 568 217 145 13 +163

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The nature of oxide film formed on the metal surface plays in
important role in oxidation corrosion.

(i) STABLE OXIDE LAYER

A stable oxide layer behaves as a protective

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

(ii) UNSTABLE OXIDE LAYER

Unstable oxide layer is mainly produced on the surface of

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

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

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

Example: Molybdenum oxide is volatile.

(iv) POROUS OXIDE LAYER

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

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 The ratio of the volume of the oxide formed to
the volume of the metal is called pilling-
bedworth ratio.

R = Md/nmD

Where M - mass of metal oxide

m - atomic weight
d - density of the metal
D - density of the scale
n- number of metal atoms in a formula of the scale

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(PILLING-BEDWORTH RULE contd)

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 porous and non-
protective.
Example: Oxides of alkali and alkaline earth metals.

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

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

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

metal then there will be protective oxide film formation.
Example: Oxides of Al, Pb, Ni, etc.

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 P B ratios of metals
Metal Metal oxide RPB
Calcium Calcium oxide 0.64
Magnesium Magnesium oxide 0.81

Aluminium Aluminium oxide 1.28

RPB < 1: the oxide coating
layer is too thin, likely broken
Lead Lead(II) oxide 1.28
and provides no protective
Platinum Platinum(II) oxide 1.56 effect e.g. Mg
Zirconium Zirconium(IV) oxide 1.56
RPB > 2: the oxide coating
Hafnium Hafnium(IV) oxide 1.62 chips off and provides no
Nickel Nickel(II) oxide 1.65 protective effect e.g. Fe
Iron Iron(II) oxide 1.7
Titanium Titanium(IV) oxide 1.73
1 < RPB < 2: the oxide coating
is passivating and provides a
Chromium Chromium(III) oxide 2.07 protecting effect
Iron Iron(II,III) oxide 2.10
Iron Iron(III) oxide 2.14
Silicon Silicon dioxide 2.15
Tantalum Tantalum(V) oxide 2.47

Vanadium Vanadium(V) oxide 3.25

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 To Note.
For good oxidation resistance the oxide should be adherent
to the surface
Adherence of the oxide
= f(the volume of the oxide formed :
the volume of metal consumed in the oxidation)
= f(Pilling-Bedworth ratio)

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 Gases like SO2, CO2, Cl2, H2S etc induce corrosion action on metals
Corrosion effect depends on the chemical affinity between the metal
and the gas.
The degree of attack by gases depends on the formation of protective
or non-protective films on the metal surface.
(1) If the film is non-porous or protective, the intensity of attack
decreases. Eg. AgCl film attack of Cl2 on Ag
(2) If the film is porous or non-protective, the surface of the whole metal
is gradually destroyed.
Eg. Dry Cl2 gas attack on Sn formation of volatile SnCl4 fresh
surface is exposed for further attack

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Oxidation resistant materials

As oxidation of most metals cannot be avoided the key is to form a

protective oxide layer on the surface
The oxide layer should offer a high resistance to the diffusion of the species
controlling the oxidation
The electrical conductivity of the oxide is a measure of the diffusivity of the
ions (a stoichiometric oxide will have a low diffusivity)

Alloying the base metal can improve the oxidation resistance

E.g. the oxidation resistance of Fe can be improved by alloying with
Cr, Al, Ni
Al, Ti have a protective oxide film and usually do not need any alloying

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 CORROSION BY HYDROGEN

(a) HYDROGEN EMBRITTLEMENT:

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

Corrosion caused by the exposure of metal to hydrogen

environment.
Hydrogen in atomic state diffuses into the metal matrix
and collects in the voids present in the metal.
The hydrogen atoms combine to form H2 gas.
A very high pressure is developed, which results in cracks
and blisters on metal. This process is called hydrogen
embrittlement.

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(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 decrease in carbon
content in steel is termed as
Decarburisation of steel.

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 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.

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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.
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 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.

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(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.

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

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

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 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.

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Bolt and nut made of the same metal is preferred.
Why?
It is preferred in practice, because galvanic
corrosion is avoided due to homogeneous metals (no
anodic and cathodic part).

Prevention:
Selection of metals & alloys
Insulating dissimilar metals
Using inhibitors
Applying cathodic protection

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Copper Zinc Joint

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Few more examples for galvanic/bimetallic corrosion

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 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).

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.

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At anode (less aerated) corrosion occurs
M M2+ +2e-
At cathode (more aerated part) OH- ions are
produced
O2 +H2O + 2e- 2 OH- 12/4/2017 54
Examples for differential aeration
corrosion

Pitting or localized corrosion

Crevice corrosion
Soil corrosion
Fencing Corrosion
Waterline Corrosion

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(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
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The rate of corrosion will be more, when the area of
cathode is larger and the area of anode is smaller. A small
hole or pit is formed on the surface of the metal.

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

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

Net reaction is
Fe2+ +2OH- Fe(OH)2 Fe(OH)3
This type of corrosion is called pitting.
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 Why are dust particles so corrosive?

Dust particles are not corrosive in themselves unless they are from
corrosive environments.

Dust particles have the tendency to hold moisture and create a

concentration cell at their location.

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 If a crevice between different metallic objects
or between metal and non-metallic material is
in contact with liquids, the crevice becomes the
anodic region and suffers corrosion.
This is due to less oxygen with crevice area.
The exposed areas act as the cathode.

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 Differential aeration corrosion may also
occur in different parts of pipeline.
Buried pipelines or cables passing from one
type of soil to another, example from clay
(less aerated) to sand (more aerated) may get
corroded due to differential aeration.

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 A wire fence in which the areas where the wires cross are
less aerated than the rest of the fence and hence corrosion
occurs at the wire crossings, which are anodic.

Other examples for differential aeration corrosion

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

(ii) Lead pipeline passing through clay to cinders undergo

corrosion. Since the pipeline under cinders is more aerated,
it gets corroded easily.

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 An employee opens his tiffin box on the road
side to see, whether he is going to office, or
coming back from office.

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Rate and extent of corrosion depends
mainly on
i. Nature of the metal
ii. Nature of the environment

The Nature of the metal

A) Position in EMF series

The extent of corrosion depends upon the

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

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.
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(c) Purity of the metal
The 100% pure metal will not undergo any type
of corrosion.
But, the presence of impurities in a metal
create heterogeneity and thus galvanic cells are
sets up with distinct anodic and cathodic area
in the metal.
Higher the percentage of impurity, faster is the
rate of corrosion of the anodic metal.

Metal components subjected to unevenly

distributed stresses are easily corroded.

Even in a pure metal, the areas under stress

tend to be anodic and suffer corrosion.
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(e) Nature of the Corrosion Product

If the corrosion product is soluble in

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

On the other hand, if the corrosion

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

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

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 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.

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 Significant hazard for corrosion of concrete in soil occurs
when:
organic matter is >12% and clay is <10% and pH (1:5
soil:water) is <5.1, or pH (1:5 soil:CaCl2) is <4.3;
clay is <35% and pH (1:5 soil:water) is <4.6, or pH (1:5
soil:CaCl2) is <3.9; or
salinity >15.6 dS/m ).
Other significant soil conditions contributing to concrete
corrosion include significant amounts of sodium and/or
magnesium sulfates. These mineral properties of soil can
only be detected by XRD.
Extra care must be taken to protect buried iron or steel where a
rust hazard occurs.

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Potential-pH Diagrams (Pourbaix Diagrams)
Graphical representations of the domains of stability of metal
ions, oxides, hydroxides, etc. in aqueous solution.

Potential

pH

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

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

1. Proper Designing
A major factor in the corrosion failure of a component
is a faulty geometrical design.
Some important design principles are:
1) Avoid crevices
2) Avoid residual moisture
3) Avoid galvanic corrosion
Galvanic corrosion can be prevented by the following
methods,
a) Use electrical insulators
b) Introduce an easily exchangeable corroding places
c) Avoid protruding parts.
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(1) MATERIAL SELECTION
(selection of proper material for a particular
corrosive service)

Metallic [metal and alloy]

Nonmetallic [rubbers (natural and synthetic),
plastics, ceramics, carbon and graphite, and wood]

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 Other than Ni, Cr and C, the following alloying elements
may also present in stainless steel: Mo, N, Si, Mn, Cu, Ti,
Nb, Ta and/or W.

Main alloying elements (Cr, Ni and C):

1. Chromium
Minimum concentration of Cr in a
stainless steel is 12-14wt.%
Structure : BCC

* Note that the affinity of Cr to form Cr-carbides is very

high.

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2. Nickel
Structure: FCC (austenite forming element/stabilize
austenitic structure)
Added to produce austenitic or duplex stainless
steels. These materials possess excellent ductility,
formability and toughness as well as weld-ability.
Nickel improves mechanical properties of stainless
steels servicing at high temperatures.
Nickel increases aqueous corrosion resistance of
materials.

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3. Carbon

Very strong austenite forming element (30x more

effective than Ni). i.e. if austenitic stainless steel
18Cr-8Ni contains 0.007%C, its structure will
convert to ferritic structure. However the
concentration of carbon is usually limited to
0.08%C (normal stainless steels) and 0.03%C
(low carbon stainless steels to avoid sensitization
during welding).

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 Dust particles and man-made pollution CO, NO,
methane, etc.
Temperature high T & high humidity accelerates
corrosion.
Rainfall excess washes corrosive materials and
debris but scarce may leave water droplets.
Proximity to sea
Air pollution NaCl, SO2, sulfurous acid, etc.
Humidity cause condensation.

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 Wall thickness allowance to accommodate for corrosion
effect.
Avoid excessive mechanical stresses and stress concentrations
in components exposed to corrosive mediums.
Avoid galvanic contact / electrical contact between dissimilar
metals to prevent galvanic corrosion.
Avoid sharp bends in piping systems when high velocities
and/or solid in suspension are involved erosion corrosion.
Avoid crevices e.g. weld rather than rivet tanks and other
containers, proper trimming of gasket, etc.

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 Avoid sharp corners paint tends to be thinner at sharp
corners and often starts to fail.
Provide for easy drainage (esp tanks) avoid remaining
liquids collect at bottom. E.g steel is resistant against
concentrated sulfuric acid. But if remaining liquid is
exposed to air, acid tend to absorb moisture, resulting in
dilution and rapid attack occurs.
Avoid hot spots during heat transfer operations localized
heating and high corrosion rates. Hot spots also tend to
produce stresses SCC failures.
Design to exclude air except for active-passive metals and
alloys coz they require O2 for protective films.
Most general rule : AVOID HETEROGENEITY!!!

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 Provide barrier between metal and environment.
Coatings may act as sacrificial anode or release substance
that inhibit corrosive attack on substrate.
Metal coatings :
Noble silver, copper, nickel, Cr, Sn, Pb on steel.
Should be free of pores/discontinuity which creates
small anode-large cathode leading to rapid attack at
the damaged areas.
Sacrificial Zn, Al, Cd on steel. Exposed substrate
will be cathodic & will be protected.
Application hot dipping, flame spraying, cladding,
electroplating, vapor deposition, etc.
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 Surface modification to structure or composition by use
of directed energy or particle beams. E.g ion implantation
and laser processing.
Inorganic coating : cement coatings, glass coatings, ceramic
coatings, chemical conversion coatings.
Chemical conversion anodizing, phosphatizing, oxide
coating, chromate.
Organic coating : paints, lacquers, varnishes. Coating liquid
generally consists of solvent, resin and pigment. The resin
provides chemical and corrosion resistance, and pigments
may also have corrosion inhibition functions.

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No Environment Proper material
1 Nitric acid Stainless steels
2 Caustic Nickel and nickel
alloys
3 Hydrofluoric acid Monel (Ni-Cu)
4 Hot hydrochloric acid Hastelloys (Ni-Cr-
Mo) (Chlorimets)
5 Dilute sulfuric acid Lead

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 No Environment Proper material
6 atmospheric exposure Aluminium
7 Distilled water Tin

8 Hot strong oxidizing Titanium

solution
9 Ultimate resistance Tantalum

10 Concentrated sulfuric Steel

acid

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2. Cathodic Protection
The principle involved in cathodic
protection is to force the metal to be
protected to behave like a cathode.
Since, there will not be any anodic area on
the metal, corrosion does not occur.

There are two types of cathodic protection.

Sacrificial anodic protection method
Impressed current cathodic protection
method.

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SACRIFICIAL ANODIC PROTECTION METHOD

In this method, the metallic structure to be

protected is made cathode by connecting it
with more active metal (anodic metal).
So that all the corrosion will concentrate
only on the active metal.
The artificially made anode thus gradually
gets corroded protecting the original metallic
structure.
Hence this process is otherwise known as
sacrificial anodic protection.

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Examples of sacrificial anode
This method is used for the protection of
ships and boats.
Sheets of zinc and magnesium are hung
around the hull of the ship.
Zinc and magnesium being anodic to
iron get corroded.
Since they are sacrificed in the process
of saving iron (anode), they are called
sacrificial anodes.

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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.

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Zinc wrapped against an Iron bar

Oil rigs use blocks of Aluminium

at the foot of every Iron pillar to
prevent corrosion

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 Applications

Jetty- A structure that projects into a body of water to influence the

Current or tide to protect a harbour or shores from storms or erosion

Zinc marine environment; Al & Mg - soil 12/4/2017 97

*Hull chassis of a ship, made
of steel (propeller made of
bronze)

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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.

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The anode is surrounded by backfill
(containing mixture of gypsum, coke,
sodium sulphate) to improve the
electrical contact between the anode and
the surrounding soil.
APPLICATION OF IMPRESSED CURRENT
PROTECTION
This type of cathodic protection is
applied to open water-box coolers, water
tanks, buried oil and water pipes,
condensers, marine piers, transmission
line towers, etc.,

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 Steel when submerged
in sea water has a
normal potential of
-500mV to -600mV

By using Impressed
current, the potential
can be raised to -750 mV

Reference electrodes
are employed to check
the potential of structure 10
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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.

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Soil corrosion Soil corrosion
effects are not effects are taken
taken in to in to account.
account.
This is most This method is
economical well suited for
method especially large structures
when short-term and long term
protection is operations.
required.

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 DEAERATION
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.

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 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.

The acidic character of the corrosive

environment (due to presence of H2S, HCl, CO2,
SO2, etc) can be neutralized by spraying alkaline
neutralisers (like NH3, NaOH, lime etc).

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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.
They work by removing electrons from the metal,
thereby pushing it into positive region where an
oxide film spontaneously forms
Inhibitors are classified in to three types,
ANODIC
CATHODIC
VAPOUR PHASE 12/4/2017
10
6
 ANODIC INHIBITORS

Chromates, phosphates, nitrite, nitrate,

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 can produce severe corrosion.

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 CATHODIC INHIBITORS

In acidic solution, the main cathodic

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

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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 Na2SO3 or by deaeration.
Salts of Zn, Mg, Ni are employed as they
form insoluble metallic hydroxide which
forms impermeable self barriers.

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Vapour phase inhibitors are organic inhibitors which
readily sublime and form a protective layer on the
metal surface.

Example : Dicyclohexyl ammonium nitrite,

Benzotriazole, dicyclohexylamine, cyclohexylamine.

Vapour phase inhibitors are used in the protection

of machineries, sophisticated equipments, etc.
which are sent by ships.
When these inhibitors come in contact with the
metal surface, the vapor of these salts condenses
and is hydrolyzed by any moisture to liberate
protective ions
The condensed inhibitor can be easily wiped off from
the metal surface. 11
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 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.
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 Protective
coatings

Inorganic coating Organic coating

Metallic coating 1. Paints
Chemical 2. Varnishes
Conversion 3. Enamels
4. Ceramic
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 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.
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 Alkali Cleaning To remove old paints that are
soluble in alkaline medium using chemicals like
NaOH, Na3PO4 etc. After cleaning, the metal is
washed with 1% chromic acid solution.

Acid pickling and etching Base metal is dipped

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

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

Cathodic coating:
It is produced by cathodic coating metals
(Sn, Cr, Ni) on Fe surface based on the
relative positive electrode potential of coat
metal.
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 Hot dipping
Electroplating Cu, Cr, Ni, Au, Ag

11
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 It is one of the common method of applying
metallic coating on the surface of base metals.
Hot dipping is a process of coating the base metal
by immersing it in the molten coat metal.
Examples: Galvanizing and Tinning

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Galvanizing: Fe or steel is coated with a
thin coat of Zn by immersing in molten Zn
to prevent rusting.
Fe or steel base metal is cleaned by acid
pickling using dil. H2SO4 (60-90 0C) for
15-20 min.
Base metal dipped in molten Zn (430 0C)
and then passed through rollers to
correct the thickness of the film.
NH4Cl flux used to protect the surface of
molten Zn from oxide formation.
Annealed at 250 0C and cooled slowly
Coating of Iron pipes, screws, bolts,
wires, etc.
Poisonous for utensils that store food
stuffs
11
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 11
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Tinning: In this process tin is coated over mild
steel sheets immersed in molten tin (Sn).
The sheet is subject to acid pickling and passed
through a bath of molten tin covered with a
flux of ZnCl2.
After coating, the sheet is passed through palm
oil to protect from oxidation
Finally the sheet is passed to roller to get
uniform thickness.
It is used for the coating of steel, Cu and brass
sheets that store food stuffs.

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 An electrochemical process where metal ions are
transferred from a solution and are deposited as
a thin layer onto surface of a cathode.
The setup is composed DC circuit with an anode
and a cathode sitting in a bath of solution that
has the metal ions necessary for coating or
plating
Electroplating can enhance;
Chemical properties---increase corrosion resistance
Physical properties---increase thickness of part
Mechanical properties---increase tensile strength &
hardness

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 Scientists now able to apply constant
current electricity to their experiments
In 1805, Italian chemist Luigi Brugnatelli,
successfully electroplated silver medals
with gold
Brugnatelli's inventions were kept secret
by the French Academy of Sciences and Wikienergia.com

did not become used in general industry

until English and Russian scientists
independently discovered technique 35
years later
1940 first patent for electroplating
awarded, and soon factories in England
were mass producing silver plated items,
including teapots, brushes and utensils
www.dinendecor.com/ 12
12/4/2017 2
Copper Cathode is reduced Nickel Anode is oxidized
(accepts electrons) (gives us electrons)

Ni2+ ions within solution attracted to Copper cathode

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Electroplating of Copper on metal surface
Electrolyte: (3-5%) H2SO4 / (15-30%) CuSO4
Anode: Pure Cu metal or Graphite (inert)
Cathode: Metal to be coated
Additive: Boric acid or gelatin

Ionization reaction of electrolyte is observed,

CuSO4 Cu2+ + SO42-
H2SO4 2H + SO42-
+

On passing current, Cu2+ + 2e- Cu

(at cathode)

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Objectives of electroplating:

(i) To increase the resistance to corrosion and

chemical attack of the plated metal.
(ii) To obtain a polished surface
(iii) To improve hardness and wear resistance
Example: Electroplating of Cu, Au, Ag, Cr, Ni, Sn
etc.,
Uses of electroplating:
(i) It is often used in electronic industries for
making printed circuit boards, edge
connectors, semiconductor lead-out
connection
(ii) It is also used in the manufacture of
jewelery, refrigerator, electric iron etc. 125
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 Surface cleaning for strong adherence
Concentration of electrolyte Moderate conc. Is preferred
for uniform coating
Conductivity and stability of electrolyte - Good
Thickness of the deposit for decorative purpose thin
coating and for corrosion protection multiple uniform
coating.
Current density (current per unit of the base metal)
should be low for uniform controlled deposition
Additives: Ensure strong adherence and mirror smooth
coating.
pH of the electrolytic bath between pH 4.0 - 5.5

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 PVD Coating (Physical Vapor Deposition)
CVD Coating (Chemical Vapor Deposition)

Physical Vapour Deposition, PVD a group of vacuum coating

techniques that are used to deposit thin film coatings that
enhance the properties and performance of tools and
machine components.

PVD coatings are used in a vast array of industries and

thousands of applications as diverse as "self-cleaning"
windows, medical implants, cutting tools, decorative
fittings and Formula 1 racing parts.
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Difficult to Easy Can be clean
handle nm scale
Poor control of Good geometry
Trap dirt and voids geometry control
In the interface
Trap dirt and voids Expensive
In the interface 12
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 12
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12/4/2017 130
Need for Vacuum

12/4/2017 131
 PVD PROCESS

PVD is a process to produce a metal vapor that can be deposited

on conductive materials as a thin highly adhered pure metal or
alloy coating.

The process is carried out in a vacuum chamber at high vacuum

(10-6 torr).

PVD coatings involve atom-by-atom, molecule-by-molecule, or

ion deposition of various materials on solid substrates in vacuum
systems.

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 PVD PROCESS
contd

Single or multi-layer coatings can be applied during the same

process cycle.

Additionally the metal vapor can be reacted with various gases to

deposit Oxides, Nitrides, Carbides or Carbonitrides.

The coating method involves purely physical processes such as high

temperature vacuum evaporation or plasma sputter bombardment
rather than involving a chemical reaction at the surface to be
coated.

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H2 = 50 psi PVD Chamber
N2 = 15 psi

Substrate
Ni film

Heater

Suction valve
N2
(or) Ni Source
2000oC
H2
To vacuum pump

12/4/2017 11:35 AM 134 13

Nanotechnology 12/4/2017 4
 Titanium Nitride coated punches
Aluminium Titanium
Carbonitride coated

Aluminium Titanium Nitride coated

Drill Bits Gear Hobber 13

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 13
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 13
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 Description of different types of PVD coating

Cathodic Arc Deposition: An electric arc is used to vaporize

material from a target. The vaporized material condenses
on a substrate, forming a thin film.

Evaporative deposition: In which the material to be

deposited is heated to a high vapor pressure by electrically
resistive heating in "low" vacuum.

Sputter deposition: In which a glow plasma discharge

(usually localized around the "target" by a magnet)
bombards the material sputtering away as a vapor.

Ion plating: In which the material is heated to a high vapor

pressure and a plasma is established to ionize the
evaporating species. These species physically implant into
the substrate producing strong coating bond.

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Steps involved in a conventional PVD Process

The surface parts to be coated are first cleaned. The

cleaning process varies depending on the level of
quality from the electroplater, substrate material and
geometry.

The parts are loaded into the vacuum chamber on

custom fixtures designed to optimize the chamber load
size and ensure coating uniformity.

The vacuum chamber is evacuated to 10-6 torr (high

vacuum) to remove any contaminants in the system.

The vacuum chamber is backfilled with an inert gas

argon.
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A high current, low voltage arc is initiated on the
target (solid material used for deposition). The metal
is evaporated and instantaneously ionized.

These metal ions are accelerated at high energies

into the vacuum through an inert gas or reactive gas
and subsequently deposited on the part.

The basic properties of the metal being evaporated

remain unchanged during the metal deposition cycle.

Changing the volume of gas and type of gas during

the reactive deposition cycle changes the nature of
the coating.

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 Some examples

Zirconium nitride (ZrN) is a hard, yellow-gold colored

coating with exceptional wear and corrosion
resistance, used in plumbing and door hardware
industry.

Introducing measured amounts of nitrogen into the

chamber during the zirconium deposition cycle
produces zirconium nitride.

Chromium nitride is produced in much the same way.

Simply by adding an additional gas such as acetylene

(C2H2), you can create chromium carbonitride. This
gives a gray to black color.
14
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 TiN Gold
ZrN Gold
TiAlN Brown
TiCN Silver
CrN Silver
DLC Black

DLC Diamond like carbon

Coating processes are performed at 300 0C or upto 2800 0C.

The higher temperature processes usually produce optimum
coating properties but sometimes results in softening of
substrates especially steel.

Thickness usually in the range of 1 to 2 m.

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 Sputtering is physical removal of atoms by incoming
ions
Coating can be done for both conductive (DC) and
non-conductive materials (RF)
DC sputtering the workpiece and substance to be
coated are connected to high voltage dc power supply.
Vacuum chamber is filled with controlled amount of
argon gas to establish a pressure of 10-4 torr.
The supplied direct current energizes the chamber
creating a plasma between the work piece and the
material to be coated.
The argon atoms get ionized and accelerated to
bombard on the workpiece resulting in the sputtering
of atoms, which are transported and coated on the
substance 14
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Fundamentals of Sputter deposition

14
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 Sputter Deposition

characterize process by sputter yield (S)

S = number ejected / number incident

14
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 Plasma Production
light
Power Gas flow

PLASMA

gas
(ng) excited atoms
and molecules
Electrons
ions
Wall Wall
radicals,
molecular fragments
reaction
secondary
products electrons

substrate

14
pumping pumping
12/4/2017 6
PVD Sputtering tool

14
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 Description of sputtering process

Sputtering: Sputtering is a process whereby coating material

is dislodged and ejected from the solid surface due to the
momentum exchange associated with surface bombardment
by energetic particles.
Gas ions are accelerated by a high voltage, producing a glow
discharge or plasma
A source (the cathode, also called the target ) is bombarded in
high vacuum by gas ions
Atoms from the target are ejected and move across the
vacuum chamber
Atoms are deposited on the substrate to be coated and form a
thin film.

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 Bounce back :
when very low energy (<5eV); when the
collision is head-on or nearly so
Embedded :
when much higher energy (>10KeV), the
impinging particles are most likely to be
embedded in the target, which is the basis
of Ion Implantation
If energy level is between the two
extremes:
some fraction of the energy of the
impinging ions is transferred to the solid
in the form of heat, and lattice damage
another fraction of such energy causes
atoms from the surface to be dislodged
and ejected into the gas phase----
Sputtering

14
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 Uniform thickness over large area.
Simple thickness control.
The alloy composition maintains stoichiometry with
the original target composition.
Deposition rates do not differ a great deal from one
material to another.
Sputtering-cleaning prior to initiating film deposition.
The surface is not again exposed to ambient after
such cleaning.

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Metals: Al, Cu, Zn, Au, Ni, Cr, W, Mo, Ti Alloys Ag-
Cu, Pb-Sn, Al-Zn, Ni-Cr
Nonmetals: graphite, MoS2, WS2, PTFE
Refractory oxides: Al2O3, Cr2O3, Al2O3-Cr2O3, SiO2,
ZrO2-Y2O3
Refractory carbides: TiC, ZrC, HfC, NbC, Tic-Ni, Tic-
ZrC
Refactory nitrides: TiN, Ti2N, ZrN, HfN, TiN-ZrN,
TiN-AlN-ZrN
Refractory borides: TiB2, ZrB2, HfB2, CrB2, MoB2
Refactory silicides: MoSi2, WSi2, Cr3Si2

15
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 15
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Add reactive gas to chamber during deposition (evaporation or
sputtering)
oxygen, nitrogen

Chemical reaction takes place on both substrate and target

can poison target if chemical reactions are faster than sputter
rate

Adjust reactive gas flow to get good stoichiometry without

incorporating excess gas into film

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Classifications of thin-films based on their applications
Thin-film property Typical applications
category
Optical Reflective/antireflective coatings
Interference filters, Decoration (colour,
luster), Memory discs (CDs),
Waveguides
Electrical Insulation, conduction, Semiconductor
devices, Piezoelectric drivers
Magnetic Memory discs/devices
Chemical Barriers to diffusion or alloying
Protecting against corrosion or
oxidation
Gas/liquid sensors
Mechanical Tribological (wear resistant) coatings
Hardness, Adhesion, Micromechanics
Thermal Barrier layers, Heat sinks

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 CVD process
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 vapor phase.

The complex molecule in the vapor state impinges on the

hot substrate, decomposes and forms a thin film. These
reactions are promoted by resistance 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
4. Substrate holder inside the chamber with heater (flat heater
900oC)
5. High Temperature valve to control the flow rate of complex vapour 15
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 15
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 In every case, CVD processes must:

provide a volatile precursor containing the

constituents of the film
transport that precursor to the deposition surface
encourage or avoid reactions in the gas phase
encourage surface reactions that form the film
and do it rapidly, reproducibly, and uniformly for
industrial applications

15
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 15
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Typical precursor materials

15
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 Precursor to Tantalum Nitride (TaN)

This material is a precursor for gate dielectrics in thin

film transistors (TFT) and is a component of
Photochemically formed SiOx on monolayer of TiO2

It is a good precursor to deposit lead oxide (PbO2)

It is a good precursor to deposit Zirconia (ZrO2)

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A volatile OMCVD precursor for the controlled
growth of nickel nanoparticle on silicon substrates

Uses are in high-density storage media

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 16
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 16
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 16
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 16
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ADVANTAGES

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 16
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 17
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Best wishes

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