Module 2

CORROSION AND ITS CONTROL

• Corrosion is defined as the destruction or deterioration
of metals and alloys by environment through chemical
or electrochemical changes.
• Corrosion process is the conversion of pure metal into
its undesirable metallic compounds.
• Example for corrosion : (i) Rusting of iron – reddish
brown scales on iron and steel objects due to formation
of hydrated ferric oxide, Fe2O3.3H2O.
• (ii) Green scales on copper vessels due to formation of
basic cupric carbonate.
 Why do metals undergo corrosion ?
▪When metals are extracted from their ores, they are at higher energy
state and unstable.

▪The metals have a natural tendency to revert back to their combined

state which is stable.

▪Therefore, metals react with the environment and get converted into
their compounds.

▪Hence, corrosion of metals is considered as reverse of extractive

metallurgy.
corrosion
Metal ↔ Metal ore
extraction
 Electrochemical theory of corrosion
●Corrosion process can be well explained by electrochemical theory.

●It is also known as wet corrosion.

●According to this theory, when a metal such as Iron, is exposed to

the environment, the following electrochemical changes occur.

●Large number of tiny galvanic cells are formed due to the formation
of anodic and cathodic areas on the metal.

●Anodic and cathodic areas are formed on the same metal surface
due to impurities in the metal, difference in oxygen concentration on
metal surface, cracks and crevices on the surface and residual stress
in the metal.
▪At anodic region of the metal, oxidation takes
place liberating electrons, and undergoes
corrosion.

▪The electrons released at the anodic region are

consumed at the cathodic area.

▪Oxygen of the atmosphere are reduced to OH-

ions in the presence of moisture at the cathodic
area.

▪Anodic area is corroded. Cathodic area remains

unaffected.
Anodic reaction : at the anodic area , oxidation
takes place resulting in the corrosion of iron.
Fe → Fe2+ + 2e-
Cathodic reactions : Electrons flow from the
anodic to cathodic area and cause reduction
depending on the nature of the corrosion
medium. Depending on the conditions, the most
common types of cathodic reactions are
(a)liberation of hydrogen and (b)absorption of
oxygen.
 ( a) Liberation of hydrogen takes place in the absence of oxygen.
In acidic medium and in the absence of oxygen, the cathodic
reaction is
2H+ + 2e- → H2↑

In neutral or alkaline medium and in the absence of oxygen, OH-

and H2 are formed.
2H2O + 2e- → 2OH- + H2↑

(b) Absorption of oxygen takes place in the presence of oxygen.

In acidic medium and in the presence of oxygen,
4H+ + O2 + 4e- → 2H2O

In neutral or alkaline medium, OH- are formed.

2H2O + O2 + 4e- → 4OH-
▪ At anode Fe2+ is formed and at cathode OH- is formed.

Fe2+ and OH- react forming insoluble Fe(OH)2 .

2Fe2+ + 4OH- → 2Fe(OH)2

▪ Further,
4Fe (OH)2 + O2 + 2H2O → 2[ Fe2O3.3H2O] (Yellow Rust)

3Fe (OH)2 + ½ O2 → Fe3O4.3H2O (Black Rust)

 Factors influencing the rate of corrosion
Physical state of the metal : Pure metals resist corrosion. Impure
metals are susceptible to corrosion.
With increasing impurities in metals rate of corrosion increases.
Smaller the grain size in metals corrosion rate increases.
Larger the grain size corrosion rate decreases.

Nature of the metal : The metals with lower electrode potential

values are more reactive .
Reactive metals such as K, Na, Mg, Zn, etc, undergo faster
corrosion. The metals with higher electrode potential values are
less reactive.
Less reactive metals such as silver, gold, platinum, etc, resist
corrosion.
The tendency of a metal to undergo corrosion decreases with
increase in electrode potential.
Nature of the corrosion product : The corrosion product is the
oxide of the metal which forms a layer on the surface of metal. The
corrosion rate depends on the oxide layer.
The ratio of volume of metal oxide to metal is specific volume ratio.
Greater the ratio, lesser is the rate of corrosion.

If this oxide layer is insoluble, stable, uniform and nonporous, it acts

as a protective layer preventing the further corrosion of metal.

If the oxide layer is soluble, unstable, non uniform and porous,

faster corrosion occurs in the metal.
Metals like Al, Cr and Ti are Passive metals because they develop
protective layer on the surface, preventing further corrosion.

Metals like Fe, Zn and Mg are Non passive metals because they
develop non protective layer on the surface and the corrosion rate
increases.
Area effect (Sizes of anodic and cathodic areas) : If a metal
has a small anodic area and large cathodic area ( the ratio of
anodic to cathodic area is small ) the rate of corrosion is
intense and faster at the anodic region.

This is because, the electrons liberated at smaller anode are

consumed rapidly at larger cathode increasing the corrosion
rate.

If the metal has large anodic area and small cathodic area (the
ratio of anodic to cathodic area is large) the corrosion rate
decreases at anode, because the electrons are consumed
slowly at smaller cathode.
pH : If the corrosion medium has lower pH, the rate of
corrosion is higher.

In the case of iron, between p H 3 and 10, the presence of

oxygen is essential for corrosion of iron.

If the pH is less than 3, severe corrosion occurs even in the

absence of oxygen. Corrosion of iron above pH 10 practically
ceases due to the formation of a protective coating at
higher pH.

Some metals like Al, Zn, etc, undergo rapid corrosion in

alkaline medium.
Temperature: Rate of chemical reactions increases with increasing
temperature.
Similarly rate of corrosion increases with increasing temperature
because, conductance of corrosion medium increases.
With increasing temperature, passivity of metals decreases and rate
of corrosion increases.
In hydrogen liberation type of corrosion, when temperature
increases, corrosion rate increases. In oxygen absorption type of
corrosion, the rate of corrosion decreases with increasing
temperature.
Hydrogen over voltage (HOV): Metal with low HOV on its surface ,
undergoes faster corrosion when the cathodic reaction is hydrogen
evolution type.
With lower HOV hydrogen gas is liberated easily and cathodic
reaction is faster. This makes anodic reaction also faster. When the
HOV is high cathodic reaction is slower and corrosion of metal
decreases.
 Types of corrosion

Galvanic series: An arrangement of metals and alloys in

the order of their corrosion resistance in the given
environment is referred to as galvanic series.

▪To overcome the limitations of Electrochemical series,

galvanic series is introduced.

▪Corrosion behaviour of metals and alloys are studied in a real

corrosion environment such as sea water.

▪Passivity of metals and corrosion of alloys are also considered

in the galvanic series.
Mg Active (anodic)
Zn
Al
Cd
Mild steel
Cast iron
Pb
Sn
Brass
Cu
Ni
Ag
Stainless steel
Ti
Au Noble (cathodic)
Pt
 Differential aeration corrosion
▪This is the corrosion arising as a result of the formation of oxygen
concentration cell due to the uneven supply of air on the surface of
metal.
▪This type of corrosion occurs when there is difference in concentration
of air or oxygen on the surface of a metal when it is exposed to the
atmosphere.

▪Due to the difference in concentration of oxygen on the surface of a

metal, oxygen concentration cell is formed.

▪The part of the metal exposed to high oxygen concentration acts as

cathode and the part of the metal exposed to low oxygen concentration
acts as anode. Less oxygenated region undergoes corrosion.
at the anode ( less O2 )

M → Mn+ + ne-

at the cathode(more O2)

O2 + 2H2O + 4e- → 4OH-

Some of the common Examples for differential aeration corrosion are

Part of the Nail inside the wall

Paper pin inside the paper

Window rods inside the frame

Dust particle or water drop on metal surface

Partially buried pipe line in soil or submerged in water

▪Examples for differential aeration corrosion are,
Water line corrosion and Pitting corrosion.

▪Water line corrosion occurs in ocean going

ships, water storage steel tanks, etc., in which a
portion of the metal is always under water.
 Stress corrosion
▪ It is the corrosion of a metal caused by the combined
effect of tensile stress and specific corrosive environment
on the metal.

▪The metal develops stress due to the mechanical

operations such as pressing, riveting, welding, bending and
quenching.

▪When the metal is exposed to a specific corrosive

environment, the stressed part of the metal will be more
reactive and acts as anode and the stress free part will be
less reactive and acts as cathode.
▪The stressed part undergoes corrosion. Stress free part
remains unaffected.
▪Examples for stress corrosion are, (i) season cracking of brass,
in which brass corrodes in presence of ammonia and
(ii) caustic embrittlement, in which steel corrodes in presence
of caustic alkali.

Caustic embrittlement
▪This is a type of stress corrosion occurring in presence of
sodium hydroxide (NaOH) in the boilers operating at high
temperature and pressure.

▪Caustic embrittlement occurs at stressed parts of the boiler

such as cracks, rivets, bends and joints. Boiler water usually
contains some sodium carbonate (Na2CO3), added for water
softening purposes.
▪At high temperature and pressure, the residual Na2CO3
undergoes hydrolysis producing NaOH.

Na2CO3 + H2O → 2NaOH + CO2↑

▪NaOH makes boiler water alkaline. This alkaline water

flows into the small cracks and crevices by capillary
action, where water gets evaporated leaving behind
NaOH.

▪The concentration of alkali gradually increases due to

poor circulation of water in the cracks and crevices. This
concentrated alkali dissolves iron at the stressed region,
forming sodium ferroate (Na2FeO2).

Fe + 2NaOH → Na2FeO2 + H2↑

▪This Na2FeO2 undergoes hydrolysis producing magnetite
(Fe3O4).

3Na2FeO2 + 4H2O → 6NaOH + Fe3O4 + H2

▪Sodium hydroxide is regenerated in the reaction and maintains

corrosion environment.
The corrosion continues developing cracks and making the
boiler metal brittle by the deposition of magnetite.

▪Electrochemical cell is formed in the boiler as follows:

Iron under stress / Conc.NaOH / Dil.NaOH / Iron stress free

(Anode) (Cathode)

▪The continuation of caustic embrittlement of boiler parts

results in the boiler failure or boiler explosion.
Prevention of caustic embrittlement: This can be done by
the addition of compounds such as sodium sulphate,
tannin, lignin, phosphates, etc, to the boiler water.

Corrosion control
Using Corrosion Inhibitors: corrosion inhibitors are
substances which when added in small quantities to the
corrosive environment decreases the corrosion rate.
These inhibitors reduce the anodic or cathodic reactions
by forming protective coating on anode or cathode
region.

There are two types of inhibitors: (i) Anodic inhibitors and

(ii) Cathodic inhibitors.
 Anodic inhibitors
▪These are the substances added to corrosion medium to
decrease the anodic reactions. Examples for anodic
inhibitors are the anions such as chromate, phosphate,
tungstate and molybdate.

▪Oxidation of the metal is the reaction that occurs at

anode during corrosion. These anions combine with metal
ions formed at the anodic region, forming the sparingly
soluble respective salts.

▪These compounds formed are deposited on the anodic

region forming protective coatings, preventing further
anodic reaction and corrosion.
 Cathodic inhibitors
▪These are the substances added to corrosion medium to decrease
the cathodic reactions.
▪Cathodic reactions are of two types they are, liberation of hydrogen
and absorption of oxygen.
▪The added inhibitors will prevent either hydrogen liberation or
oxygen absorption at cathode.
▪Inhibition of hydrogen liberation: The liberation of hydrogen at
cathode can be prevented by preventing the diffusion of H+ ions to
the cathode or by increasing the hydrogen overvoltage (HOV) on the
metal surface.
The diffusion of H+ ions to the cathode can be prevented by adding
the inhibitors such as urea, thiourea, mercaptans, etc.
▪The evolution of hydrogen at cathode can also be prevented by
increasing the HOV on the metal surface. The inhibitors such as oxides
of arsenic, antimony, increase the HOV and prevent hydrogen evolution
at cathode.
▪Inhibition of oxygen absorption: The absorption of oxygen can be
prevented either by removing the oxygen from corrosion medium or by
simply decreasing the diffusion rate of oxygen to cathode.
▪Oxygen can be removed from corrosion medium by adding the
reducing agents or oxygen scavengers such as hydrazine, sodium
sulphite, etc.
▪These inhibitors remove oxygen from corrosion environment by
reducing it.
N2H4 + O2 → N2 + 2H2O

2Na2SO3 + O2 → 2Na2SO4
ZnSO4 and MgSO4 are also added as inhibitors.
The Zn2+ and Mg2+ ions react with OH- ions formed at cathode
forming metal hydroxides.

Zn2+ +2OH- → Zn (OH)2

Mg2+ + 2OH- → Mg (OH)2
The metal hydroxide formed prevents diffusion of oxygen to the
cathodic region, decreasing the corrosion rate.

Cathodic protection
▪Prevention of corrosion of metal by forcing the metal to behave as
cathode by providing electrons from external source.
▪It is a method of protecting a metal or alloy from corrosion by
converting it completely into cathode.
▪Corrosion can be prevented in metals by eliminating the anodic
area and converting the entire metal into cathodic area.
 Cathodic protection can be done by the following methods:
(i) Sacrificial anode method and (ii) Impressed current method.

Sacrificial anode method

▪In this method the metal structure which is to be protected is
converted into a cathode by connecting it to a more active metal.
This active metal being more reactive acts as anode and undergo
corrosion protecting the metal structure which becomes cathode.

Zn, Mg and Al are the active metals used as anode. Since the
anodic metal corrodes to protect the metal structure this method
is known as sacrificial anode method. The consumed anodes are
replaced by new ones as and when required.
 Some of the examples are:

▪ Mg block connected to a buried oil storage tank

▪ Mg bars are fixed to the sides of ocean going ships
▪ Mg blocks are connected to buried pipe lines.

Advantages: ▪ Simple method

▪ Installation cost is less
▪ Maintenance cost is less

Disadvantage: ▪ Expenditure of replacing consumed anodes.

.

Impressed current method

▪The principle involved in this method is forcing the metal to
behave as cathode by applying external current opposite to
corrosion current.
▪In this method the metal structure to be protected is made
cathodic by connecting it to the cathode of the external source of
direct current (battery).
▪The anode of the source is connected to an inert electrode. The
entire metal structure is converted into cathode and does not
undergo corrosion. The inert anode also remains unaffected.
Graphite, Platinum, Silicon are used as anodes.

Advantages: ▪It can protect large area of metal.

▪Maintenance cost is low.
Disadvantage: ▪It is expensive because current is required for
protection of metal.
 Protective coatings
▪Protective coatings protect a metal from corrosion by acting as a
barrier between the metal and the environment.
Metal coatings: It is a type of protective coating. It is the deposition
of a protective metal on the surface of a base metal to protect the
base metal from corrosion.
▪Metal coatings are of two types: (i) Anodic coating and (ii)
Cathodic coating.
Anodic coating
▪Coating a base metal with more active metals which are anodic to
the base metal is known as anodic coating. For example, iron is
coated with anodic and more active metals such as Zn, Mg and Al.
In the anodic coating, even if there is cracks in the coating, the
base metal will not corrode, but the coating metal undergoes
corrosion because it is anodic to the base metal. Therefore, anodic
coating is also known as sacrificial coating.
▪Therefore anodic coating is also known as sacrificial coating.
▪Galvanisation of iron and steel is an example for anodic coating.

Galvanisation
▪It is a process of coating a base metal surface with zinc metal.
▪Galvanisation protects iron and steel from corrosion.
▪It is carried out by hot dipping method. It involves the following steps:
▪The metal article surface is washed with organic solvents to remove
organic impurities such as oil, grease, etc.
▪ It is washed with dilute sulphuric acid to remove rust, scales and other
deposits.
▪ The article is washed with water and air dried.
▪ The article is then dipped in a tank of molten zinc, at 4300C and
covered with ammonium chloride (NH4Cl) flux, to prevent the oxidation
of molten zinc.
▪ Then it is passed through a pair of hot rollers, to remove excess coating
of zinc and produce thin coating.
▪ In the galvanised iron or steel, even if there is cracks in the coating
the base metal does not undergo corrosion, because the exposed
part of the base metal is cathodic and the coating metal is anodic.
Therefore, coating metal corrodes.
▪ Galvanised roofing sheets, fencing wire, buckets, bolts, nuts, nails,
screws, pipes, tubes, etc, are protected from corrosion.
▪ Galvanised containers are not used for preparing and storing food
items, because zinc dissolves in dilute acids of food producing toxic
zinc compounds.

Cathodic coating
▪Coating a base metal with less active or more noble metals which
are cathodic to the base metal is known as cathodic coating. For
example, iron or steel is coated with more noble and cathodic
metals such as Cu, Ni, Sn and Ag.
 ▪The cathodic coating provides protection from corrosion only
when it is undamaged and continuous.
▪Tinning is an example of cathodic coating on iron or steel.

Tinning
▪ It is a process of coating a base metal surface with tin metal.
▪Tinning protects iron and steel from corrosion. It is carried out by
hot dipping method. It involves the following steps:
▪ The metal sheet surface is washed with organic solvents to remove
organic impurities such as oil, grease, etc.
▪ It is washed with dilute sulphuric acid to remove rust, scales and
other deposits.
▪ Then it is washed with water and air dried.
▪ The sheet is then passed through molten zinc chloride (ZnCl2)
flux,which helps the molten metal to adhere on the metal surface.
▪ It is then passed through a tank containing molten tin.
▪ Then it is passed through a series of rollers immersed in palm oil, to
remove excess coating of tin and produce thin coating. Oil prevents the
oxidation of tin coated surface.

▪ In the tin coated iron or steel, if there is cracks in the coating, the base
metal undergo corrosion, because the exposed part of the iron is anodic
and the coating metal tin is cathodic.

▪ Severe corrosion (pitting corrosion) occurs at the exposed iron surface,

because of small anodic area and large cathodic area.

▪ Tin coated containers are used for preparing and storing food items,
because tin is non toxic.
SLE: Galvanic corrosion, Waterline corrosion
and Seasonal cracking