Corrosion and its Control

CORROSION AND ITS CONTROL

Corrosion is defined as “The destruction or deterioration & consequent loss of
metals alloy through chemical or electrochemical attack by environment”.
Ex: 1. Rusting of iron – a reddish brown scales formation on iron & steel objects. It is due to
the formation of hydrated ferric oxide [Fe2O3.3H2O].
Ex: 2. Green scales formed on copper vessels. It is due to the formation of basic cupric
carbonate [CuCO3 + Cu (OH)2].
Why do metal undergo corrosion:

• Most of the metals, except noble metals occur in the form of their ores such as oxides,
sulfides, carbonates, chlorides etc…

• The metals are extracted from these ores by reduction.

• During reduction, the energy is supplied in the form of heat or electrical energy.

• Consequently, the pure metals are relatively higher energy state compared to their
corresponding ores & they have natural tendency to revert back to their combined
state. i.e, lower energy stable state.

• Therefore, when metals are used in various forms, they combine with the constituents
of the environment & get converted into their compounds. Thus, corrosion of metal
can be considered as reverse metallurgy.
Problems faced by corrosion:

• 20% of the total iron production is used to replace the corroded iron materials.

• Direct losses: The corrosion in metal objects like equipment, instruments, chemical
plants & structures etc., may make them inefficient, ineffective & useless.

• Indirect losses: When a building & bridge collapse due to corrosion problem the loss
includes loss of human life, properties & lost of subsequent repair & alternate
arrangement.
Therefore, corrosion is a great issue & we should know the corrosion, its types,
mechanism of corrosive control by various methods should be known.
The corrosion is broadly classified in to two classes.
1. Dry corrosion / Direct chemical attack: It takes place generally in the absence of
moisture. Here constituents of corrosion medium directly combine with the metal
based on their chemical affinity to form respective compounds.

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2. Electrochemical theory of corrosion/ Wet corrosion:

(Ex: Rusting of Iron)
It is also called as wet corrosion since aqueous medium or moist air is required for
corrosion to take place & most of the problems are explained based on this electrochemical
theory of corrosion.
According to this theory, corrosion of metals takes place due to formation of tiny
galvanic cells. i.e, the formation of separate anodic and cathodic regions on the same metal
surface or when two different metals are in contact with each other in the presence of a
conducting medium (moisture).
At anodic region oxidation reaction takes place & metals converted in to its ions,
liberating electrons consequently, and metal undergoes corrosion at the anodic region.
At the cathodic region reduction takes place, metal atoms at the cathodic region
unaffected & some constituents of the corrosion medium take part in the cathodic reactions.
The electron liberated at the anodic region migrates to cathodic region to form corrosion
current. The metal ion liberated at the anode & some anions formed at the cathode move
towards each other through the conducting medium & form a corrosion product. Corrosion
continuous as long as both anodic & cathodic reactions takes place simultaneously.
Corrosion Reactions:
At anodic region:
At the anode simple oxidation reaction takes place in which metal atoms are
converted into their ions liberating electrons.
M Mn+ + ne-
Ex: when iron undergoes corrosion
Fe Fe2+ + 2e-
At cathodic region:
The cathodic reactions are more complicated therefore reaction depends upon the
constituents present in the corrosion medium & the nature of the corrosion environment.
There are two types of cathodic reactions will take place:
1. Liberation of Hydrogen
2. Absorption of Oxygen
1. Liberation of hydrogen: It takes place in the absence of oxygen & liberation of
hydrogen at the cathode.
a) In acidic medium in the absence of O2
2H+ + 2e- H2

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b) In neutral/alkaline medium in the absence of O2 hydroxide ions are formed with the
liberation of H2.
2H2O + 2e- 2OH- +H2
2. Absorption of oxygen:
It takes place in the presence of oxygen.
a) In acidic medium & in the presence of oxygen.
4H+ + O2 + 4e- 2H2O
b) In neutral / alkaline medium in the presence oxygen, hydroxide ions are formed.
2H2O + O2 + 4e- 4OH-
Corrosion of iron produces Fe2+ & OH- at anode and cathode sites respectively. These
diffuse towards each other to form insoluble Fe (OH)2 [ferrous hydroxide].
In high level oxygen environment, it is further oxidized to ferric oxide & the yellow
rust is hydrated ferric oxide.
2Fe2++ 4OH- 2Fe (OH)2
4Fe (OH)2 + O2 + 2H2O 2[Fe2O3. 3H2O]
In the presence of limited oxygen, ferrous hydroxide is converted into magnetic oxide
of iron (Fe3O4) known as black rust.
3Fe (OH)2 + 1/2O2 Fe3O4. 3H2O

FACTORS INFLUENCING THE CORROSION RATE:

1. Physical state of the metal:
The rate of corrosion is affected by the physical state of the metal. Such as grain
surface, stress on the metal etc., if the grain size is small, it is easily soluble & greater is the
rate of corrosion & visa versa. The area under stress is more susceptible to corrosion because
stressed area is of higher energy than stress free area.
2. Nature of the metal:
The tendency of a metal to undergo corrosion is depends on the nature of the metal. In
general, the metals with lower electrode potential values are more reactive than the metals
with higher electrode potential values. The more reactive metals are more susceptible for
corrosion. Thus, the tendency of metal to undergo corrosion decreases with in increases in
electrode potential.
Example: The active metals like K, Na, Mg, Zn etc., with low electrodes potential values are
highly susceptible for corrosion. The noble metals like gold, silver & platinum etc… with
higher electrode potential value are less susceptible for corrosion.

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3. Nature of the corrosion product:

The nature of the corrosion product largely decides the rate of further corrosion. If the
corrosion product deposited on the surface of the metal may or may not be act as protective
film.
If the corrosion product deposited is insoluble, stable, uniform & nonporous, it act as
protective film & prevent the metal surface from further corrosion.
If the corrosion product is soluble, unstable, non uniform & porous, the corrosion is
continuously takes place therefore the fresh metal surface continuously exposed to the
corrosion environment.
When the corrosion product formed is either soluble in the medium or formed away
from the anodic & cathodic sites, then also the corrosion product does not have any protective
value.
Example: In oxidizing environment, metals like Aluminum, Chromium, Titanium
etc… are higher passive as their oxides form protective films on the metal surface & metals
such as Iron, Zinc, and Magnesium do not form any protective film & are highly
susceptibility for continuous corrosion.
4. Area effect:
The rate corrosion is greatly influenced by the relative size of anodic & cathodic
areas. If the metal has a small anodic area & large cathodic area (i.e, ratio of anodic to
cathodic area is small), then the corrosion rate is more intensive & faster at the anodic region.
As the ratio decreases the rate of corrosion increases rapidly. Because at the anode the
oxidation takes place & electrons are liberated. At the same time cathode consume the
electrons when anode is smaller & cathode region is larger all the electrons liberated at anode
is rapidly consumed at the cathode region, this makes the anodic reaction faster & leads to
increase in overall corrosion rate.
Example: If a broken coating of tin on iron acts as anodic region rest of the large tin
coating as cathodic region. Because of small anodic to cathodic area the corrosion is high.
Therefore, the iron bolts are not used in the copper boilers.
5. PH:
If PH of the corrosion medium is lower, the corrosion rate is fast. Because of hydrogen
liberation type reaction which increases the reaction rate of the cathode, in turn increases the
reaction rate of anode & therefore overall corrosion rate will increases. But some metals like
Al, Zn, etc., undergo fast corrosion in basic/alkaline medium & also PH solution decides the
type of cathodic reaction.

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6. Temperature:
The rate of corrosion increases as the temperature increases. Increase in temperature
increases the conductance of the corrosion medium which increases the corrosion rate. But in
case of corrosion resistant passive metals, the rise in temperature decreases the passive range
& there by increases the corrosion rate.

TYPES OF CORROSION:
Depending upon the conditions, metals undergo corrosion by different mechanisms,
giving rise to different type of corrosion cases.
They are,
1. Galvanic corrosion (Differential metal corrosion)
2. Differential aeration corrosion (Pitting corrosion)

GALVANIC CORROSION (DIFFERENTIAL METAL CORROSION)

Differential metal corrosion occurs when two dissimilar metals are in contact with
each other in a corrosive conducting medium. The two metals differ in their tendencies to
undergo oxidation, the metal with lower electrode potential acts as anode & the metal with
higher electrode potential will acts as cathode. The potential difference between two metals is
the driving force for corrosion & anodic metal undergoes corrosion & cathodic metal is
unattacked.
Reactions:
At the anode: M Mn+ + 2e-
At the cathode: Depending upon the nature of the corrosion environment the cathode reaction
may be either hydrogen evolution or oxygen absorption type.
2H+ + 2e- H2(g)
O2 + 2H2O+ 4e- 4OH-
Examples
1. Steel/iron, screws/rivets in copper sheet.
2. Steel pipe connected to copper plumbing.
3. Lead antimony, solder around copper wire.
The rate of this corrosion depends on potential difference between two regions, ratio of
anodic to cathodic area, environmental factor & passivity.

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GALVANIC SERIES:
An arrangement of metals & alloys in the order of their corrosion resistance in the
given environment is called as galvanic series. Different metals have different tendencies to
corrode. The electrochemical series gives list of elements with respect to their standard
electrode potential value. This is not enough to predict corrosion, because electrochemical
series does not take passivity into account.
Ex: 1. Chromium (-0.56) is less noble than iron (-0.44) in the electrochemical series, but
chromium is a passive metal & it imparts excellent corrosion resistance, when its alloy in
with iron.
2. Aluminum (-1.66) & titanium (-1.75) are anodic to iron, but they exhibit grater
resistance against corrosion. Therefore, to overcome these limitations a series called
galvanic series was introduced. The corrosion studies on various metals & alloys were
performed in various environment & the metals are arranged in the order of their
corrosion resistance.

DIFFERENTIAL AERATION CORROSION:

This type of corrosion occurs when a metal surface is exposed to differential air
concentrations/oxygen concentrations. The part of the metal exposed to higher oxygen
concentration acts as cathodic region & the part of the metal exposed to lower oxygen
concentration acts as anodic region. Consequently, poorly oxygenated region undergoes
corrosion.
Reactions:

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At the anode (less O2 concentration):

M M2+ +ne-
At the cathode (more O2 concentration):
O2 + 2H2O + 4e- 4 OH-
Corrosion of metals arising as a result of the formation of oxygen concentration cell due to
the uneven supply of air on the metal surface is known as differential aeration corrosion.
Examples:
1. Window rods nail inside the frame suffer corrosion.
2. Part of nail inside the wall, being exposed to low oxygen concentration than the
exposed part.
3. Paper pins inside the paper gets corroded & the exposed part is free from corrosion.
4. Metal under dust, dirt, scale or water undergoes corrosion.
5. Pipeline partially buried in solid.

PITTING CORROSION:

Pitting corrosion is one of the most destructive forms of corrosion, because if its
localized & intense form of corrosion & failure often occur with extreme suddenness. It
forms a pit or pin hole around which the metal is unaffected.
Pitting is explained by small anodic area & large cathodic area, resulting in
acceleration corrosion at the anodic area. This corrosion generally initiated by the deposition
of dust, dirt, scale or drop of water etc., or due to the breakdown of the protective film. The
metal below the deposit exposed to lower oxygen concentration acts as anode & the
remaining metal exposed to high oxygen concentration acts as cathode.
Once the corrosion product formed, it further provides conditions for differential
aeration below the corrosion product & the remaining metal part. The pit grows & ultimately
causes the failure of the metal.
Example: Breakdown of small tin coating on iron gives rise to small anodic & large cathodic
area, this results in accelerated pitting corrosion at the exposed part.

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CORROSION CONTROL
The most important and commonly used methods are discussed below:
1. Protective coatings
2. Using inhibitors
3. Cathodic protection
4. Anodic protection

PROTECTIVE COATINGS:
Application of protective coating is one of the important methods of corrosion
control. The protective coating protects the metal from corrosion by acting as a barrier
between the metal & the corrosion environment.
The main types of coatings applied on the metal surface are:
a) Metal coating
b) Inorganic coating
c) Organic coating

a) Metal coating:
Deposition of a protective metal over the surface of a base metal is called metallic
coating. It is a valuable & well-tried method for improving the corrosion life of the
underlying metal.
Metal coatings are applied by electro depositing, flame spraying, cladding, hot
dipping, diffusion coating & vapor deposition.
There are two class of metallic coatings are there. They are,
*Anodic coating
*Cathodic coating

ANODIC COATING:
Anodic coating is done by coating a base metal with more active metal such as zinc,
magnesium & aluminum. The most important characteristic of anodic coating is that, even if
the coating is ruptured, the base metal does not undergo corrosion. Because the exposed
surface of a base metal is cathodic with respect to the coating metal & the coating metal
preferentially undergoes corrosion. The protection is ensured as long as the anodic coating is
still present on the surface. Therefore, anodic coating is also known as sacrificial coatings.

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Galvanization is a familiar example for anodic coating & is extensively used to protect iron &
steel objects.
GALVANISATION:
The process of coating a base metal surface with zinc metal is called Galvanization.
Galvanization of steel is favored because of its low cost & eases of application. It is carried
out by hot dipping method & involves the following steps.

• The metal surface is washed with organic solvents to remove organic matter on the
surface.

• Rust and other deposits are removed by washing with dil.H2SO4.

• Finally, the article is well washed with water & air dried.

• The article is then dipped in a bath of molten zinc, maintained at 425 - 430oC &
covered with a flux of ammonium chloride to prevent the oxidation of molten zinc.

• The excess of zinc on the surface is removed by passing through a pair of hot rollers,
which wipes out excess of zinc coating & produces a thin coating.
Galvanization is used extensively to protect iron from corrosion in the form of roofing
sheets, fencing wire, bar bend wire, buckets, bolts, nuts, screws, pipes, tubes etc., Galvanized
steel reinforcement is used in building construction, where high degree of corrosion
resistance is required.
Galvanized articles are however not used for preparing & storing food stuffs, since
zinc dissolves in dilute acids producing toxic compounds.

CATHODIC PROTECTION:
Cathodic protection is a method of protecting a metal or alloy from corrosion by
converting completely into cathodic & no part of it is allowed to act as anode.
Principle: Metals undergo corrosion by electrochemical process with the formation of
anodic and cathodic regions in contact with each other. The corrosion of metal takes place at
the anodic region where as, the cathodic region is unaffected. Therefore, corrosion can be
prevented by eliminating the anodic site & converting the entire metal into cathodic area.
This can be achieved by two methods,
1. Sacrificial anode method
2. Impressed current method

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1. SACRIFICIAL ANODE METHOD:

In this method the protected metal structure is converted into a cathode by connecting
it to a more active metal. This active metal acts as an auxiliary anode. Zinc, magnesium,
aluminium are the common auxiliary anodes used in this method. These metals act as anode
& undergo corrosion, protecting the metal surface.
Since the metals are sacrificed to protect the metal structure, therefore the method is
known as sacrificial anode method. Exhausted sacrificial anodes are replaced by now one as
& when required.
Examples:
a) A magnesium block connected to a buried oil storage steel tank.
b) Magnesium bars are fixed to the sides of ocean-going ships to act as sacrificial anodes.
c) Magnesium blocks are connected to buried pipelines.

SACRIFICIAL ANODE METHOD

Advantages:
1. The method is simple.
2. Low installation cost.
3. Minimum maintenance cost.
4. Does not require power supply.
Disadvantages:
1. Involves recurring expenditure for replacement of consumed anodes.
2. Poorly coated structure may require many anodes.

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ANODIZING
Process of anodizing of Aluminium

1.Anodizing is generally produced on non-ferrous metals like Al, Zn, Mg and their alloys.
2.Al when made cathode allows the passage of electrons but cease to conduct when it
is made anode in aqueous solution of chromic acid (or) H2SO4.This is because of the
formation of a thin layer of Al2O3 over the metal.

Anodizing of Aluminum
Anode: Aluminium
Cathode: Cu / Steel/Lead
Electrolyte: 5-10 % chromic acid or 10 % H2SO4
Temperature: 35 oC
Voltage: 40 V
Current density: 100 A /m2
Electrode reactions
At anode
(Oxidation): 2Al + 3H2O → Al2O3 + 6 H+ + 6e-
At cathode
(Reduction): 6H+ + 6e- → 3H2
Overall reaction: 2 Al + 3H2O → Al2O3 + 3H2

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1. The metal after pre-treatment is made to act as anode and steel copper or lead acts as
cathode.
2. The electrolyte consists of 5-10 % chromic acid.
3. The temperature of the bath is maintained at 35oC
4. A current density of 100 A/m2 is applied which oxidizes the outer layer of Al to Al2O3
5. An oxide layers of Al2O3 with a thickness 2-8 μm is formed.
6. For higher thickness 10% H2SO4 is used as the electrolyte
Application
Anodized articles are used as soap boxes tiffin carriers, window frames, nameplates
decorative object.

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