Corrosion

Definition
Gradual attack on a metal
Chemical or electrochemical reaction by its
surroundings
Metal is converted into its oxide, salt or
some other compound that is,
deterioration and loss of material due to
chemical attack

Factors influencing corrosion

1.

Chemical nature of the metal

2. Internal structure
3. Working conditions or
environment like stresses,
temperature or concentration
4. Presence of dust, dirt or foreign
matter
5. Surface film

Contd.
6.

Blow holes, inclusions and trapped

gases
7. Distribution of secondary phases
8. Nature of engineering applications
9. Eddy electric currents
Types of corrosion:
(i) general types (ii) specific types

General types
1.
2.
3.
4.

Direct corrosion
Electrochemical corrosion
Galvanic corrosion
high-temperature oxidation

Specific types
1. uniform corrosion
2. Pitting corrosion
3. Intergranular corrosion
4. Atmospheric corrosion
5. Stress corrosion
6. Corrosion fatigue
7. Erosion corrosion

Contd.
8.

Fretting & selective corrosion

9. Soil corrosion
10. Microbial corrosion
11. Liquid metal corrosion
12.Crevice corrosion

Direct corrosion

Essentially ordinary chemical attack

Happens due to chemical reactions between
the metals and corrosive solutions such as
acids
Metal is dissolved; no protective layer that
could inhibit corrosion is formed
Corrosion is uniform, relatively high and can
be measured in standard units, e.g.,
milligrams per square decimeter per day
(mdd)

Examples for direct corrosion

Acid pickling used to clean metal
surfaces and etching (involves
chemical attack)
Reactions of dry chlorine, H2S, O2,
other dry gases with dry metalsthese are examples for direct
chemical attack and also considered
as redox reactions

Control
By adding some inhibiting chemicals in the

corrosive solution
They act as barriers between the metal
involved and the environment

Electrochemical corrosion
Takes place at or near room temperature
Takes place due to reaction of metals with
water or with aqueous solutions of salts,
acids or bases
Involves transfer of electrons
Flow of electricity from certain areas of the
metal surfaces to other parts through a
medium which conducts electricity

Contd.
Potential

difference must exist between different

metals or between two areas on the surface of
metal
Metal surfaces develop anodic and cathodic
sites
Anode is the portion of the metal surface that is
corroded and dissolved as ion electron leaves
from that site and enter the environment
This is called anodic oxidation

Contd.
Cathode is that portion at which current
returns to the metal from the environment
Reduction takes place at cathode and
the metal is not affected at cathode
Highly pure single phase metals corrode
at a slower rate than impure metals and
alloys containing many phases

Electrochemical Series
Metals are arranged in the order of their
standard electrode potentials
The ability of metals to resist corrosion is
to some extent dependent upon their
position in the electrochemical series

Galvanic Series
The various standard electrode potentials
listed in the electrochemical series were
measured under certain chemical conditions
at a particular concentration and temperature
The electrodes were completely clean and
free from oxide films
Therefore, not always possible to predict
which will be anode and which will be cathode

Contd.
For practical purposes, electric potentials of
many materials are obtained in a single
environment, viz., sea water
These when arranged in the decreasing order
of oxidation potential is called galvanic series
Pair of metals from this series connected
together in sea water, the metal which is
higher in the series would be anode
Farther they are apart, greater the corrosion
tendency

Galvanic series

Anodic end (corroded end)

Mg>Zn>Al>Cd>Al alloys>mild
steel>alloy steel>cast
iron>stainless steel>muntz
metal>yellow brass>Al brass>red
brass>Al bronze>CuNi
alloys>inconel>Ni>Ag>Stainless
steel(passive)>monel>titanium
Cathodic end(protected)

Origin of potential difference on

metal surfaces
Factors:

(i) internal (ii) external

Internal factors:
Micro structure and composition of metal
such as:
1. Different crystal orientation (metal is
polycrystalline)
2. presence of small amounts of minute
impurities within the microstructure, often
concentrated at the grain boundaries

Contd.
3. Change in concentration of
alloying components in different
points of the metal (that may occur
as a result of the original casting
technique or as a consequence of the
precipitation of very fine particles)
4. Presence of more than one phase
in the metal as in the case of
multiphase metals

External factors
Associated with metals as well as corrosive

environments
1. Residual and applied stress in the metal
particularly after mechanical working
2. Presence of dust, dirt, soot and other
foreign bodies on the metal surface

External factors
3. Presence of protective oxide films on metal

surface before their contact with a corrosive

environment
4. Presence of adsorbed gas on the metal
surface

External factors
5. Local changes in the concentration of an

electrolyte, the presence of dissolved gases,

the presence of some agents influencing
polarization and depolarization of the anodic
and cathodic areas distributed on the surface
of the corroding metal
6. Temperature differences in the body of the
electrolyte leading to the formation of thermal
gradients , the degree of agitation of a
corrosive environment, and the differential
lighting of some portion of a metal surface

Polarization at the electrodes

Individual electrode potentials, for ex.
Cu and Zn electrodes, change from
normal value when current flows
between two electrodes
Change in potential as a result of flow
of current is known as the polarization
of the electrode

Polarization at the electrodes

Polarization causes the solution
potential (difference in potential
between metal and solution) of the
anode to become more cathodic and
that of the cathode to become more
anodic (i.e. Direction reversed and
reverse current is produced)

Polarization at the electrodes

Hence, the potential difference
between the electrodes steadily
decreases and the amount of current
in the closed circuit diminishes
Polarization at the electrodes is due
to concentration polarization, over
voltage, or the presence of surface
film on the electrodes

cells
(i) Electrochemical cells (ii) galvanic cells
Electrochemical cells electrolysis takes place;
anode is +ve and cathode is ve
Electrical
chemical
Galvanic cells Chemical
electrical
Anode is ve (oxidation); cathode is +ve
(reduction)
(-)
(+)
Anode
cathode

Galvanic cell
Daniel cell
Zn

+
current

oxidation

e-

ZnSO4

Cu
Reduction

CuSO4

Zn Zn2++2e-

Cu2++2e-

Cu

Concentration polarization
As reaction proceeds near electrodes, ionic

concentration near each electrode becomes different

from that of the main body of the electrolyte
Reason: slowness in diffusion of ions in the
immediate vicinity of the electrodes
At anode (-ve electrode), concentration of the metal
ions will gradually increase and the anode potential
will be more +ve, while at cathode (+ve electrode),
concentration of the +ve ions will decrease and the
cathode potential will be more negative

Overvoltage
This

is the excess voltage than the actual

voltage of a single electrode while current
passes through it.
Ex: hydrogen over voltage hydrogen evolution
is slow therefore, more H+ ions will be near the
electrode more emf
This will be opposite to the normal emf
H+ + e H; H+H
H 2(adsorbed)
H2(adsorbed)
H2(evolved)
Plays an important role in corrosion processes

Presence of films
Protective films are formed on the
electrodes both at the cathode and the
anode as a result of the combined effect
of the electrode reactions and the action
of the environment
Resistance between cathode and anode
increases and the rate of diffusion
decreases

Galvanic cells
Metal of high electrode potential is placed
in water and is electrically connected to
another metal of much lower electrode
potential
A current will flow through the wire
connecting the electrodes called
galvanic cells
Electrochemical corrosion involves a
transfer of electrons

Factors increasing the rate of

corrosion in a galvanic cell
1. A large difference in electrode
potential between anode and cathode
2. increased acidity of the electrolyte
Increased oxygen concentration in
the electrolyte around the cathode

Summary of electrode
reactions in galvanic cells
Mn++ne- (metal
Anode: M
dissolves)

H+ + OH Cathode: H2O
2H+ + 2eH2

H2O + O2 + 2e2OH
Oxygen absorption at the cathode uses
more electrons; hence rate of corrosion
increases

Mechanism of
electrochemical corrosion
Involves transfer of electrons
Electrons must flow between
anodic and cathodic areas
Anodic reaction: always dissolution
of metals and formation of ions
Cathodic reaction: may involve two
different processes depending on
the nature of corrosive
environment evolution of
hydrogen gas, absorption of oxygen

Hydrogen evolution mechanism

When corrosion environment is acidic such
as acid industrial waters and the
concentration of dissolved oxygen is low,
hydrogen evolution type of corrosion occurs
Example: steel tank containing acid
industrial wastes and a small copper scrap
in contact with the steel plate

Hydrogen evolution mechanism

Contact between the piece of copper and steel vessel in
the presence of acid electrolytes shown in the figure forms
a corrosion cell; Cu becomes cathodic and steel anodic
Hence steel portion in contact with Cu is corroded
Fe
Fe2+ + 2e H+ ions present due to dissociation of solution take up
these electrons and bubbles of hydrogen gas is evolved
from the cathode as follows:
2H+ + 2eH2
Therefore, hydrogen evolution type corrosion is simply the
displacement of hydrogen ions from the solution by metal
ions

Acid waste

H
2
Fe2+

H+

Steel tank

H+

Fe2+

Small Cu scrap

Electron flow from anodes

Oxygen absorption
mechanism
Corrosion

mechanism is most likely to

occur when dissolved oxygen is
present in the electrolyte
Ex: Fe is corroded by a neutral
aqueous solution of electrolytes in the
presence of oxygen
Steel plate lying on the ground and is
exposed to atmosphere

Drop of water

crack

cathode
rust
Film or scale

rust
Fe2+

Fe2+

e-

Steel plate

e-

Anode at crack

Contd.
In course of time, oxide layer will form on
the surface of the steel plate and drops of
water may collect over a small crack in the
oxide film present on the surface of the
steel (figure)
Water acts as the electrolyte, crack as the
anode and the scale protected steel as
cathode

Contd.

At the anode(i.e. crack), the steel goes into solution as ions

according to the following equation:
Fe
Fe 2+ + 2eAt the large cathodic area (scale protected steel plate) the
electrons flow from the anode and are intercepted by the
oxygen atoms present in the atmosphere, and in the presence
of water drop.
OH- ions are formed according to the following reaction:
H2O +1/2 O2 + 2e2OHFe2+ ions migrate to the edge of the water drop, combine with
OH- ions, form ferrous hydroxide, Fe(OH)2 or brown rust
Then oxidised to ferric hydroxide, Fe(OH)3 or hard rust
Corrosion will take place as long as there is oxygen supply
available.