CORROSION AND ITS CONTROL

CORROSION AND ITS CONTROL

 Most of the metals (Except Au, Pt) exist in nature in

combined state as their Oxides due to its reactivity.
 These are reduced to get Metals (Extraction of metals)
 Extraction of the metals is a reduction process.
 When the metals are exposed to environment
destruction starts at the surface.
 This destruction may be due to direct attack of
chemical or electrochemical
 Reverse of extraction of metals is called Corrosion
 “Any process of destruction or deterioration of metals
through chemical or electro chemical attack by its
environment is called Corrosion”
 Corrosion is a phenomenon of gradual
deterioration of metals or its alloys by the
action of environment to their respective
chemical compounds.
Theories of corrosion:

1. Dry (Chemical or Direct) Corrosion

2. Wet corrosion (Electro chemical)
1) Dry corrosion or Chemical corrosion:
 This type of corrosion occurs through the direct
chemicals
 There are three main types of chemical corrosion
 Oxidation corrosion
 Corrosion by other gases (SO2, CO2, Cl2 etc.,)
 Liquid metal corrosion

Oxidation corrosion:
 It occurs by the direct attack of oxygen at low or
high temperatures on metals.
 It is caused in absence of the moisture.
 At low temperature alkali and alkaline earth metals
are rapidly oxidized and at high temperature almost
all metals (except Au, Ag, and Pt) are oxidized.
 2M 2 M2+ + 2e- (Oxidation)
O2 2 O2- (Reduction)
M + O2 Metal oxide
Mechanism:
Oxidation occurs first at the surface of the metal and the resulting
metal oxide forms a barrier.
Either metal ion diffuse out side or oxide must diffuse inwards
through the scale.
Diffusion of metal ion out side is much faster than the oxygen
diffusion
Nature of oxide formed: This oxide plays an important role in
oxidation corrosion.
1.Stable:
A stable layer is fine grained and gets adhered to the parent metal
surface.
So, it acts as protective layer
Further corrosion is prevented for these metals.
Ex.: oxides of Al, Sn, Pb, Cu, etc.
ii) unstable:
If the oxide formed is unstable, decomposes back
into the metal and oxygen.
 So, corrosion is not possible.

Ex.: oxide of Pt
iii) Volatile:
 If the oxide formed is volatile in nature it
volatizes as soon as it is formed.
 So, corrosion rate increases rapidly.

Ex.: oxide of Mo
iv) Porous: i.e., having pores or cracks. This
causes continuous corrosion.
Ex.: oxide of K, Na, etc.
This is explained based on the Pilling-Bed
worth Rule
 According to this rule “an anode is protective
or non-porous, if the volume of the oxide is
greater than the volume of metal.”
 It is explained based on the ratio of the metal
oxide volume to the metal volume.
 Porous layers usually contain PBR less than
1 and non-porous layer greater than 1.
Corrosion by other Gases:
 The gases like SO2, CO2, Cl2, H2S etc. may also cause
corrosion.
 The extent of the corrosion depends on the chemical
affinity between metal and the gas.
 The degree of attack depends on the formation of
protective or non-protective films on the metal surface.

Hydrogen corrosion:
 A different type of dry corrosion attack by hydrogen gas
on metals is known as hydrogen embrittlement. it is due
to the formation of atomic hydrogen as a result of
chemical or electrochemical reaction at metal surface.
Fe + H2S  FeS + 2H
H + H  H2
Liquid metal corrosion:
 It is due to chemical action of flowing liquid
metal at high temperature on solid metal or
alloy.
 It involves either dissolution of a solid
metal by a liquid metal; or internal
penetration of liquid metal into the solid
metal
2) WET OR ELECTROCHEMICAL CORROSION:
 This type of corrosion occurs
 Where a conducting liquid is in contact with
metal or
 When two dissimilar metals or alloys are
immersed partially in a solution.
 Two metals act as electrodes and current flows
through the conducting solution.
 At anode oxidation reaction takes place, so
anodic metal is destroyed.
 Hence, corrosion always occurs at anode.
 But the cathode is not affected.
The principle types of electrochemical corrosions
are
1) Hydrogen evolution corrosion

2) Oxygen absorption corrosion

Evolution of Hydrogen type:
 Usually corrosion occurs in acidic medium

 Fe metal converts into ferrous ions at anode by

liberation of the electrons.
 This type of corrosion causes displacement
of H+ ions from acidic solution by metal ions.
 In this type of corrosion anodes are large
areas; where as cathodes are small areas.
 Fe Fe+2 + 2e- (oxidation)

These electrons flow through the metal from anode to cathode

The hydrogen ions present at cathode eliminated as H2 gas.

2H+ + 2e- H2 (Reduction)

+ +2
Fe + 2H Fe + H2
Absorption of Oxygen:
 Common example is rusting of iron in neutral
medium (NaCl)
 The surface of iron always coated with iron
oxide. If some cracks are developed on this
metal oxide, anodic areas are created; while
the well metal parts act as cathodes.
 In this type of corrosion anodes are small
areas; where as cathodes are large areas.
 At anode:
Fe Fe+2 + 2e- (oxidation)
At cathode:
The liberated electrons are absorbed by dissolved oxygen.

O2 + H2O + 2e- 2 OH-

The Fe+2 and OH- diffuse and combine to form Fe(OH)2

Fe+2 + OH- Fe(OH)2

Types of corrosion
1) Galvanic corrosion
2) Waterline corrosion
3) Soil corrosion
1) Galvanic Corrosion:
 When two dissimilar metals are electrically connected
and exposed to an electrolyte, the metal which has
higher oxidation potential values undergoes
corrosion.
 Ex. Daniel cell
 In acidic solution evolution of the H2 takes place
 While in alkaline or in neutral solution, oxygen
absorption occurs.
3) Underground or Soil Corrosion:
The corrosiveness of the soil depends on
 Soil acidity

 Degree of aeration

 Electrical conductivity

 Soil moisture

 Soil texture
 According to particle size soils are classified as
1) Gravelly or Sandy Soil:
 It is very porous and aerated. If a metal is buried in such
soil corrosion occurs similar to wet corrosion
2) Water-logged Soil:
 Amount of oxygen available is very small, but bacteria
may present and cause microbiological corrosion
3) Intermediate character corrosion:
 Fine gravel, sand and salt containing soil may
produce intense corrosion. If air pockets are present,
differential aeration corrosion may occur.
 Factors influencing the corrosion:
The rate and extent corrosion of corrosion
depends on
 Nature of metal

 Nature of corroding environment

1. Nature of the metal:
Position in galvanic series:
 When two metals are electrical contact in presence of
an electrolyte the more active metal undergoes
corrosion.
 The rate depends on the difference in their position in
galvanic series.
 Greater the difference is the faster the corrosion of
the anode.
Over voltage:
 The over voltage of the metal in the corrosive
environment is inversely proportional to corrosion
rate.
 When a metal, which occupies high position in
galvanic series, is placed in 1N H2SO4 it corrodes
and produces small EMF. If a few drops of CuSO4 is
added corrosion rate accelerates.
Purity of the metal: Impurities in the metal cause
heterogeneity and form electrochemical cells.
higher the percentage of impurity , faster is the rate
of corrosion of the anodic metal.
Physical state: The smaller the grain-size of metal is
contact with greater amount of environment, hence rate
of corrosion increases.
Nature of surface film: It can be explained based on the
specific volume ratio.
Specific volume ratio = vol. of metal oxide / vol. of metal
Greater the specific volume ratio, lesser the oxidation
corrosion rate.
2. Nature of the corroding environment:
Temperature:
 With increase of temperature of environment
reaction as well as diffusion rate increases
there by corrosion rate also enhanced.
Humidity:
 Corrosion of a metal becomes faster in humid
atmosphere is that gases and vapours, water
vapour acts as electrolyte, system becomes
electro chemical cell.
PH:
 Acidic media is more corrosive than alkaline
and neutral media.
e.g. : Zn suffers minimum corrosion at PH = 11,
which is rapidly corroded even in weakly acidic
solution.
Formation of O2 concentration cell:
with the increase in supply of oxygen to the moist
metal surface the corrosion is promoted.
less oxygen concentration parts become anodic,
more gets cathodic leads to formation of o 2
concentration cell. Anodic part suffers from
corrosion.
at cathode
2 H2O +O2 +4 e-  4 OH-
at anode
Fe  Fe 2+ + 2e- ( corrosion )

 CATHODIC PROTECTION

 The principle of this method is that the base

 Metal to be made as cathode by connecting
 it to powerful anode metal plate
 There are two types
 1.Sacrifical anodic protection
 The metallic structure to be protected is connected
through a metallic wire to a more anodic metal so that
all the corrosion will take place only the anodic metal.
 Metals commonly used as sacrificial anodes are zinc
aluminum mg.
 Applications
 This methods are to protect underground pipelines
cables, protection of water tanks
 2.Impressed current cathodic protection
 In this method an impressed direct current
is sent in the opposite direction of the
corrosion current to nullify it.
 Usually a battery is an one terminal
connected with an insoluble anode graphite
electrode immersed in a backfill containing
coke, gypsum, sodiumsulphate.
 The terminal of the battery is connected to
the metallic structure to be protected, witch
act as the cathode
Application;
 This method usually applied to underground
water pipe lines, oil pipe lines, marine piers
ships
 PROTECTIVE COATINGS
Introduction:
a) Protective coatings function as a continuous physical barrier
between the coated surface and the environment
b) Besides corrosion protection, it also acts as a decorative
smooth polished surface.
Surface coatings-methods of application on metals:
1) Hot dipping
it is a process of coating the base metal by immersing it in the
molten coat metal.
Ex: Galvanising, Tinning, Metal cladding, Electro plating.
Methods of application of metallic coatings:
Galvanising
TINNING:
METAL CLADDING:
 ELECTRO PLATTING:

Anode Cathode
Article to be Protected
Organic surface coatings:
 These are inert organic barriers applied on
metallic surfaces and other constructional
materials for both corrosion protection and
decoration.
The protective value of such a coating depends on
1) Its chemical inertness to the corrosive
environment,
2) Its good surface adhesion,
3) Its impermeability to water, salts and gases as
well as ,
4) Its proper application method.
Paints :
 Paint is a mechanical dispersion mixture of
1 or more pigments in a “vehicle”
 “vehicle” is a liquid, consisting of non
volatile, film forming material, drying oil
and highly volatile solvent, thinner.
 when a paint is applied to a metal surface
the thinner evaporates, while the drying oil
slowly oxidizes forming a dry pigmented
film.
Constituents of paints :

Pigments,

Drying oil,

Thinner driers,

Extenders/filters,

Plasticizers,

Anti skinning agents.

(1) pigments:
 Provide Capacity to paint
 Desired colour
 Wear resist & abrasion resist.
 Impermeability to moisture
 give protection to by reflecting U.V light
 White:White lead, Zinc ride
 Red: Red lead, chartered
 Blue: Prussian blue
 Black: Carload black

Characteristics of good pigment:

 Chemically insert
 Non toxic
 Opaque
 Cheap
 Freely mixable with film forming constituent.
(2) Drying Oil:
Are glycerol esters of high mol. weight. Fatty acids
present in animal and vegetable oils.
Ex:- linsed oil, soyabean, dehydrated caster oil.
Dying oil, linsed oil
Semi drying oil, soybean oil, Fish oil
Non drying oil, mustard oil, Sunflower oil
Function of Drying Oil:
 Main Film forming constituent
 Vehicle or medium
 Toughness
 Adhesion
 Water-proof ness
(3) Thinner:
 Reduces paint viscosity to suitable level

 Dissolve additives in vehicle

 Suspend pigments

 Increase penetration power and elasticity

of paint film
 Help in drying of the paint as it evoparates.

Eg :Turpentine, mineral spirits, benzene.

(4) Drier:
 O2 carrier catalysts
 Accelerate drying process through oxide,
polymerization and condensation.
Eg: Resonates, Tungstates and naphtates of Co, Mn, Ph
and Zn.
(5) Extenders (or) Fillers:
 To reduce the cost
 To reduce cracking of dry paint film
 To fill void in film
 Act as carrier few pigment colour.

(6) Plasticisers:
 To provide elasticity to film
 To minimize its cracking

Ex: Triphenyl phosphate, Tricresyl phosphate

(4) Drier:
 O2 carrier catalysts
 Accelerate drying process through oxide, polymerization and
condensation.
Eg: Resonates, Tungstates and naphtates of Co, Mn, Ph and Zn.
(5) Extenders (or) Fillers:
 To reduce the cost
 To reduce cracking of dry paint film
 To fill void in film
 Act as carrier few pigment colour.
(6) Plasticisers:
 To provide elasticity to film
 To minimize its cracking
Ex: Triphenyl phosphate, Tricresyl phosphate
(7) Anti skinning agents:
 Poly hydroxy phenols.
 Pigment Volume Concentrator( PVC) =
in paint.
 If PVC is more
 Bind annuity decrease
 Wash ability
 Opacity of white paint is created by
difference in refractive indices vehicle
and pigment.