Corrosion and Its Control Oct 15

Engineering Chemistry (revised edition)
ISBN: 978-81-265-4475-2
Copyright©2014 Wiley India Pvt. Ltd. All Rights Reserved
Corrosion in Metals and Alloys
The destruction of metals or alloys by surrounding environment through

chemical or electrochemical changes.
Causes of Corrosion
Corrosion is the deterioration of materials by chemical interaction with their

environment. The term corrosion is sometimes also applied to the degradation
of plastics, concrete and wood, but generally refers to metals. The most familiar
example of corrosion is rusting of iron exposed to the atmospheric conditions.

ISBN: 978-81-265-4475-2
ISBN: 978-81-265-4475-2
Types of Corrosion
1. Dry Corrosion (Direct Chemical Attack)
There are three main types of dry corrosion.
1.Oxidation corrosion (reaction with oxygen):
The overall reaction can be given by

ISBN: 978-81-265-4475-2
Mechanism for oxidation corrosion

ISBN: 978-81-265-4475-2
The oxide layer formed can be
1. Stable: e.g. Protective oxide film which prevents further
oxidation of metal e.g., aluminium, lead, copper and tin
2. Unstable: The metal oxide formed decomposes back to
metal and oxygen, so no oxidation corrosion is observed
on these metals e.g. Silver, Pt and gold
3. Volatile: Metal oxide formed volatizes as soon as it is
formed, resulting in further rapid corrosion e.g.
molybdenum oxide
4. Porous: Porous metal oxide layer traps atmospheric
oxygen e.g. Oxide films of lithium, sodium and
magnesium

ISBN: 978-81-265-4475-2
2. Corrosion by other gases such as Cl2, SO2, H2S, NOx:
In dry atmosphere, these gases react with metal and form
corrosion products, which may be protective or non-protective.
Dry Cl2 reacts with Ag and forms AgCl which is a protective layer,
while SnCl4 is volatile. In petroleum industries at high
temperatures, H2S attacks steel forming FeS scale which is porous
and interferes with normal operations.
2. Liquid metal corrosion:
In several industries, molten metal passes through metallic pipes
and causes corrosion due to dissolution or internal penetration. For
example, liquid metal mercury dissolves most metals by forming
amalgams, thereby corroding them.
Wet corrosion (Electrochemical theory of corrosion)
Metal comes in contact with a conducting liquid or when two dissimilar metals
are immersed dipped partly in a solution.

ISBN: 978-81-265-4475-2
The reactions involved in the galvanic cell are as follows:
1.Anodic reaction: Metal undergoes oxidation (corrosion) with positive release

of electrons:
2.Cathodic reactions: These reactions are dependent on the constituents of the

corrosion medium.
•If the solution is aerated and almost neutral, oxygen is reduced in presence of
H2O to OH− ions.
•If the solution is deaerated and almost neutral, H2 is liberated along with OH−
ions.
•If the solution is deaerated and acidic, H+ ions are reduced to hydrogen gas

ISBN: 978-81-265-4475-2
3. The metal ions formed at the anode combine with hydroxyl ions and form
the corresponding metallic hydroxide Fe(OH)2, which further gets oxidized
to hydrated ferric oxide [rust].
In the presence of limited oxygen, black rust is formed as follows:

ISBN: 978-81-265-4475-2
ISBN: 978-81-265-4475-2
Types of Electrochemical Corrosion
Differential Metal Corrosion (Galvanic Corrosion)
When two dissimilar metals are in contact in corrosive environment.

ISBN: 978-81-265-4475-2
Other examples of differential metal corrosion (galvanic corrosion) include the
following:
1.Buried iron pipeline connected to zinc bar.

2.Steel pipe connected to copper plumbing.
3.Steel propeller shaft in bronze bearing.
4.Zinc coating on mild steel.
5.Lead–tin solder around copper wires.
Preventive Measures
1.Placing a thin layer of an insulator between two metals or materials.

2.Selecting materials having very less potential difference.

ISBN: 978-81-265-4475-2
Differential Aeration Corrosion (Concentration Cell Corrosion)
When metal is exposed to differential air or oxygen concentration.

ISBN: 978-81-265-4475-2
The examples of differential aeration corrosion include:
1.Half-immersed iron plate in aqueous solution.

2.Steel pipe carrying any liquid exposed to atmosphere.
3.Ocean going ships.
4.Steel storage tanks.
Preventive Measures
1.Using metallic coating, electroless plating or chemical conversion methods.

2.Maintaining the material’s own protective fi lm.
3.Controlling the chemistry of fluids and using inhibitors.

ISBN: 978-81-265-4475-2
Waterline Corrosion
Waterline corrosion: (a) Water storage tank and (b) ocean going ship.

ISBN: 978-81-265-4475-2
Pitting corrosion
Localized attack on iron surface in chloride medium
Preventive Measures
1.Preparing surfaces with best possible finish. Mirror-finish resists pitting best.
2.Removing all contaminants, especially free-iron by passivation.
3.Designing and fabricating to avoid trapped and pooled liquids.

ISBN: 978-81-265-4475-2
Other types of corrosion
1. Intergranular Corrosion:
Generally observed in alloys, this corrosion involves an attack on
the grain boundries of a metal of alloys, where the formation of
corrosion products takes place (like carbides in steel)
Cathode: Chromium –rich grain centers
Anode: Grain Boundary (Chromium Carbide)
Stainless Steel (18% Cr and 8% Ni) contaning more than 0.1% C
2. Soil corrosion: Underground pipes, cables, tank
bottoms, etc., get corroded due to moisture, pH of
soil, ionic species like chlorides and micro-organisms
like bacteria. It is further enhanced by differential
aeration of various parts of the soil.

ISBN: 978-81-265-4475-2
ISBN: 978-81-265-4475-2
Small ratio of anodic to cathodic region leading to high rate of corrosion
Large ratio of anodic to cathodic region leading to low rate of corrosion.

ISBN: 978-81-265-4475-2
Corrosion Control Methods
1. Design and material selection: number of angles, corners, edges etc.

should be minimized
2. Protective coatings: prevents surface corrosion

ISBN: 978-81-265-4475-2
3. Cathodic protection:
(1) Sacrificial Anode Method:
(2) Impressed current method.

ISBN: 978-81-265-4475-2
4. Corrosion inhibitors:
Anodic Inhibitors: Additions of anions such as chromate,
tungstate, molybdate, etc.
Cathodic Inhibitors: Inhibiting the cathodic reactons which
involves the liberation of hydrogen in acidic solutions and OH-
Organic cathodic inhibiotors such as amines, mercaptans,
thioureas, sulphoxides form a protective layer on cathodic
regions and prevent the evolution of hydorgen
Inorganic cathodic inhibitors: Sulphates of Mg, Mn, Ni and Zn are
used in neutral or alkaline medium. These inhibitors react with
OH- ions liberated at cathode forming insoluble hydroixides
which form protective films over cathodes.
The End

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Engineering Chemistry (revised edition)

The destruction of metals or alloys by surrounding environment through

Corrosion is the deterioration of materials by chemical interaction with their

Engineering Chemistry (revised edition)

1. Dry Corrosion (Direct Chemical Attack)

There are three main types of dry corrosion.

1.Oxidation corrosion (reaction with oxygen):

The overall reaction can be given by

Engineering Chemistry (revised edition)

Engineering Chemistry (revised edition)

Engineering Chemistry (revised edition)

Engineering Chemistry (revised edition)

1.Anodic reaction: Metal undergoes oxidation (corrosion) with positive release

2.Cathodic reactions: These reactions are dependent on the constituents of the

Engineering Chemistry (revised edition)

In the presence of limited oxygen, black rust is formed as follows:

Engineering Chemistry (revised edition)

Differential Metal Corrosion (Galvanic Corrosion)

When two dissimilar metals are in contact in corrosive environment.

Engineering Chemistry (revised edition)

1.Buried iron pipeline connected to zinc bar.

1.Placing a thin layer of an insulator between two metals or materials.

Engineering Chemistry (revised edition)

When metal is exposed to differential air or oxygen concentration.

Engineering Chemistry (revised edition)

1.Half-immersed iron plate in aqueous solution.

1.Using metallic coating, electroless plating or chemical conversion methods.

Engineering Chemistry (revised edition)

Engineering Chemistry (revised edition)

Engineering Chemistry (revised edition)

Engineering Chemistry (revised edition)

Large ratio of anodic to cathodic region leading to low rate of corrosion.

Engineering Chemistry (revised edition)

1. Design and material selection: number of angles, corners, edges etc.

2. Protective coatings: prevents surface corrosion

Engineering Chemistry (revised edition)

Engineering Chemistry (revised edition)

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