Corrosion

Professor Andreas
Chrysanthou
School of Engineering and
Technology,
University of Hertfordshire

1
Corrosion

Contents

Introduction

Types of corrosion

Corrosion mechanisms

Corrosion prevention

2
 Definition of corrosion
Corrosion is defined as the chemical
degradation of metals
 Why does corrosion occur?
Metals like iron, aluminium and
titanium are found in nature as
oxides; in other words their oxide
form is energetically more stable than
the pure metal form. Corrosion is the
process that takes them to this more
stable form.
As engineers we want to prevent or
minimise corrosion.
 Reasons for Corrosion
Concerns
Materials loss
Failure of components
Cost of corrosion (in EU countries 3-4% of GNP)
Safety
Legal requirements
Environmental pressures
Appearance of product

5
 Some examples of
structures failing due to
corrosion
Aerospace structures, cars, trains, etc.
Bridges
Buildings
Cars
Numerous other examples

Collapse of the Point

Pleasant Bridge in Ohio in
1967 due to corrosion
which led to a crack and
failure of the bridge

6
 . and some surprising
facts.
In 1979, the City of Westminster, London, reported
problems with failing lamp posts due to corrosion at
the base
- the problem was attributed to dog urine
- in recent years similar reports have emerged from
many countries

7
 Types of Corrosion
Wet corrosion occurs in the presence of
oxygen and an electrolyte (water). Both
oxygen and an electrolyte must be present for
wet corrosion to occur. This type of corrosion
is found at low temperatures. This is the type
of corrosion found in an automotive body. Wet
corrosion is the most common type of
corrosion.
Dry corrosion occurs at high temperatures
and is the type of corrosion that can be found
in aerospace/automotive engines, power
generation plants, etc.
 Why do some metals
corrode, while others are
protected?
Some metals like sodium and
potassium are very reactive and
corrode readily in air or water.
 Why do some metals
corrode, while others are
protected?
Metals like gold and platinum are
very stable and do not corrode easily.
 Why do some metals
corrode, while others are

protected?
Some reactive metals like aluminium have good
corrosion resistance because they form a stable
protective oxide on their surface. This is known as
passivity.
Some other metals (like chromium) show the
same behaviour.
The passive oxide is self-generated
spontaneously.
 Why are the oxides of
aluminium and chromium
protective against
corrosion?
Because they have good adherence
onto the surface of the metal.
Good adherence is exhibited because
the volume of the oxide per metal
atom is similar to the volume of the
metal (shown by Pilling and Bedworth
around 1930).
 Pilling-Bedworth ratio
This is the ratio between the volume of
the oxide and the volume of the metal
per metal atom in the oxide molecule.

RPB is the Pilling-Bedworth ratio,

M - the atomic or molecular mass,
n - number of atoms of metal per one
molecule of the oxide
- density
V volume
 Pilling-Bedworth ratio
If RPB is < 1, the oxide forms under
tension and cracks (example Mg).
If RPB is 1-2, the oxide adheres well
on the surface and protects the
metal (example Al, Cr).
If RPB is >2, the oxide forms
compression and cracks (example
Fe). Note the failure of iron oxide
(dark brown) due to
compressive stresses. This
exposes more metal which
subsequently corrodes.
Requirements of an oxide to
be protective
Chemical stability.
Physical stability.
Good adherence onto the metal.
No cracks.
 PILLING-BEDWORTH RATIO
EXAMPLE
Calculate the Pilling-Bedworth ratio for
aluminium. The atomic mass is 27g,
the molecular mass is 102g, the
density of Al is 2.7Mg/m3 and of Al2O3 it
is 4Mg/m3. The formula of its oxide is
Al2O3 so the number of aluminium
atoms in the molecule of the oxide is
2.
 Stainless steel
One way to protect steel is through
addition of chromium to the steel.
Chromium dissolves in the iron to form
a solid solution (the amount of carbon
is kept to a minimum).
To be stainless, the steel must contain
a minimum of 12% chromium by
weight (minimum required to cover the
entire surface with chromium oxide).
 Wet Corrosion
Also known as aqueous corrosion or
electrolytic oxidation
The
Thinning presence1a.
of steel of Anode:
water isFeessential for- wet
Fe2+ + 2e
corrosion
by uniform attack 1b. Cathode: O 2 + 2H 2 O + 4e -
4OH -

of its surface, due

to anodic and 2: Fe2+ + 2OH- Fe(OH)2
cathodic reactions
occurring 3: 4Fe(OH)2 + O2 2(Fe2O3.H2O) +
randomly 2(H2O)
wherever 4(FeO.OH) +
oxygenated water
2(H20)
is in contact with
metal

18
 Wet Corrosion is
electrochemical
e -

O2 O2 O2 O2

ZINC ANODE IRON (or STEEL)

(Zn Zn2+ + 2e-) CATHODE
Zn2+ 4OH- (2H2O + O2 + 4e-
4OH-)

Water
19
 Wet Corrosion is
electrochemical
Loss of electrons = oxidation and occurs
at a site called the anode
Metal Metal ions + electrons
in the case of iron, Fe Fe2+ + 2e-
Gain of electrons = reduction and
occurs at a site called the cathode
Note that an anodic reaction can take
place only if there is a corresponding
cathodic reaction (and vice versa)
 Factors Affecting the Rate of
Temperature Corrosion
(In general, high temperature higher rate, but
condensation, etc. can lead to the reverse)
Oxidation Potential of the Metal
(ie. Ease with which the anodic reaction takes
place galvanic series shows relative potential)
Corrosivity of the Liquid
(presence of corrosive ions: salts Na+, Mg2+, Cl-,
+ 2- 2- 3- - -
etc. acids
3 4 H 4, CO3 , SO , PO , NO , Cl , etc. also
pH)
Presence of relative humidity and rainfall
(leading to condensation on cold metal surfaces)
21
Presence of Protective Corrosion Products
Factors Affecting the Rate of
Corrosion
Condition of the metal/alloy
(cold-working, residual stresses,
surface roughness, etc. tend to
increase the corrosion rate)