Mechanical and Production Engineering Department Faculty of Engineering

UNIVERSITY OF MAURITIUS
FACULTY OF ENGINEERING

MECHANICAL AND PRODUCTION ENGINEERING DEPARTMENT

ENGINEERING MATERIALS CIVE 1002 & CIVE 1101

LECTURER: Mr. S. Venkannah
What is corrosion?
Corrosion is the deterioration of a substance (most commonly a metal) or its properties when the
substance/metal reacts with the surrounding environment. It is a process whereby a substance/metal forms a
compound that is more stable, (for metals, this means returning to its natural ore form.)

What causes corrosion?
Corrosion is frequently caused by an electro-chemical reaction that is similar to the reaction that makes a battery
work (the flow of electrons from the anode (positive end) to the cathode (negative end)). The surrounding
environment most often provides the necessary ingredients (heat, moisture, acids, chemical contaminants, for
example salt, nitrogen and sulfur oxides, etc.), that creates the electro-chemical reaction on the surface of
substance/metal.

If a piece of iron rod is immersed in a polar solvent like water, some of the metals ions leave the crystal and go
into solution. As the metal continues to dissolve. More and more electrons are left back and a net negative
charge builds up in the metal. Similarly, the presence of excess positive ions builds up a positive charge in the
solution adjacent. These opposing electrical layers discourage further dissolution of the metal.

The potential developed by an electrode in equilibrium is a property of the metal forming the electrode.

As only potential difference can be measured in an experiment, the potential of electrode is determined against a
standard hydrogen electrode whose potential is taken to be zero.

To establish standard conditions, an electrode of the metal to be tested is placed in a 1 molar solution of its ions.
A semi permeable membrane divides the cell. For the other half of the cell a platinum electrode is placed in a 1
molar solution of hydrogen ions. A stream of hydrogen is bubbled around the platinum electrode.
If metal more reactive than hydrogen:

M ne M
n+

nH
+
+ne nH
0

The metal has a negative potential

If the metal is less reactive than hydrogen:
nH
0
- ne nH
+

M
n+
+ne M
0


The metal has a positive potential

The standard potential will be changed if the metal is not pure or if the metal ion concentration in the electrolyte
is not unity.

The potential under non standard conditions is given by:
S. Venkannah MECH 2121 & CIVE 1002/1101 November 2005

Mechanical and Production Engineering Department Faculty of Engineering

V =V
0
RT ln(M/M
+
)
nF

V
0
standard potential
M
+
Metal ion concentration in the electrolyte
M concentration of the metal in the electrode
N valency of the metal ion
F Faraday constant =96.46 kC/mole of electrons

ANODE AND CATHODE REACTIONS:
The basic types of reaction are the same whatever the rate of corrosion.

There is an anode reaction at which point metal goes into solution as an ion; i.e. it corrodes e.g.
Zn Zn
++
+2e
Fe Fe
++
+2e

Or in general M M
n+
+ne

The metal flow through the metal part until they reach a point where they can be used up (cathode reaction)
In the case of zinc in acid , the electrons combine with the hydrogen ions at the surface to form
atomic hydrogen. Most of this combines to from molecular hydrogen which bubbles off, but some
dissolves in the metal. (hydrogen attack)
2H
+
+2e 2H H
2
(g)
In the case of iron in water, the solution is neutral, and we have a reaction involving oxygen and
water using up the electrons from the anode to form hydroxyl ions
O
2
+2H
2
O +4e 4OH
-

(dissolved)

For corrosion to progress, it is essential to have both anode and cathode reaction, otherwise a charge
builds up stopping reaction.

THE RATE OF CORROSION
Metal dependent factors
The effective electropotential of a metal in solution
The overvoltage of hydrogen on the metal
The chemical and physical homogeneity of the metal surface
The inherent ability of the metal to form an insoluble protective film

Environment dependent factors.
The hydrogen ion concentration of the solution
The influence of oxygen in solution adjacent to the metal
The specific nature and concentration of other ions in solution
The ability of the environment to form a protective deposit on the metal
The rate of flow of the solution in contact with the metal
The application of cyclic stress
The temperature

Galvanic Cell
Galvanic Cell may also occur when two pieces of the same metal are placed in 2 different electrolytes or the
same electrolyte of different concentration and separated by a porous membrane/substance.
yTwo different phases in the same metal may form a galvanic couple
yGalvanic cell may be set up due to differences in concentration of the metal ion in the electrolyte
yA galvanic cell may also arise due to differences in the oxygen concentration.
S. Venkannah MECH 2121 & CIVE 1002/1101 November 2005

Mechanical and Production Engineering Department Faculty of Engineering
Passivation: Certain common engineering materials, such as Fe,Cr, Ni, Ti and Si as well as their alloys (I.e
stainless steels) exhibit a characteristic of being able to behave both as an active and passive material. Note that
in the galvanic series that several stainless steels are listed twice.

E.g. A piece of iron or steel readily dissolves in dilute nitric acid but may become resistant or passive in
concentrated nitric acid. The concentrated nitric acid oxidises the iron effectively and produces a thin protective
layer on the surface. Dilute acid is not strong enough to oxidise and hence continues the attack. If the iron in the
conc. Acid is scratched or agitated so that it strikes the container walls, a violent reaction occurs with liberation
of nitrogen oxide gas.

Polarisation: In an electrochemical cell, at the instant the anode is electrically coupled with the cathode, the p.d
is the equilibrium thermodynamic value as calculated from the std. Electrode potentials. As soon as current is
drawn from this cell, its overall potential begins to decrease as a result of various phenomena that occur at the
individual electrodes causing them to approach each other in potential. Can be created by concentration
polarisation or hydrogen overvoltage

Polarisation occurs because the diffusion rate of the ions in the solution is not fast enough to keep the electrolyte
composition throughout, the potential of the anode will shift towards the noble end. Similarly the potential of
the cathode also shifts towards the active side.

FORMS OF CORROSION:
Uniform attack- uniform intensity over the entire surface. Often leaves behind a scale or deposit. Lifetime can
be predicted.

Galvanic corrosion- Occurs when two metals or alloys having different compositions are electrically coupled
while exposed to an electrolyte.

Crevice corrosion- As a consequence of concentration differences of ions or dissolved gases in the electrolyte
solution and between 2 regions of the same metal plate.

Pit corrosion- Very localised corrosion attack resulting in small holes or pits. They normally penetrate from
the top of a horizontal surface downward in a nearly vertical direction. May be produced by the localised
destruction of a normally protective film.

Intergranular corrosion- Occurs preferentially along grain boundaries for some alloys and in specific
environments. Localised attack at and adjacent to grain boundaries with relatively little corrosion of grains.
Alloy disintegrates and loses its strength.

Selective leaching- Preferential removal of an element from a solid alloy as a consequence of corrosion
processes. E.g removal of zinc in brass leaving behind a porous material (Dezincification).

Erosion corrosion- Combined action of chemical attack and mechanical abrasion or wear as a consequence of
fluid motion. Virtually all metals are susceptible to erosion corrosion. Normally harmful to metals that
passivate.

Stress corrosion- Combined action of applied stress and a corrosive environment. Some materials that are
virtually inert in a particular corrosive medium become susceptible to this form of corrosion when a stress is
applied. E.g.
1. Most stainless steels stress corrode in solution containing chloride ions
2. Brasses are vulnerable when exposed to ammonia.

CONTROL OF CORROSION:
Selection of materials
4Use of corrosion resistant materials but depends on some other factors.

Modification to the design
4Avoid physical contact between dissimilar metals.
4Avoid differential aeration cells
4Avoid unfavourable area ratio
4Improve drainage
S. Venkannah MECH 2121 & CIVE 1002/1101 November 2005

Mechanical and Production Engineering Department Faculty of Engineering
4Avoid sharp bends and corners
Modification to the environment
4Vapour phase inhibitors
4control humidity, temperature, pH, oxygen concentration, solid or dissolved pollutants, electrolyte
velocity

Application of barrier coats
4Metallic and Non metallic coatings
4Anodic and cathodic inhibitors
4Cladding of the materials e.g. Alclad

Cathodic or Anodic protection
Cathodic protection - Protection by galvanic action is provided by connecting the structure to be protected to a
sacrificial anode which is periodically replaced.

Anodic protection- It is based on the formation of a protective passive film on metal surfaces by externally
impressed anodic currents. Many metals that display active-passive transitions, such as Ni, Fe, Cr, Ti and their
alloys, may be passivated by the proper application of controlled anodic currents which will reduce their
corrosion rate.

S. Venkannah MECH 2121 & CIVE 1002/1101 November 2005