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. Direct corrosion
2. Electrochemical corrosion
3. Galvanic corrosion
4. 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 metals- these
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 e-

- Cu
Zn +

oxidation
current Reduction Zn Zn2++2e-

Cu2++2e- Cu
ZnSO4 CuSO4

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 H2(adsorbed)
H2(adsorbed) H2(evolved)
Plays an important role in corrosion
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
Anode: M Mn++ne- (metal
dissolves)
Cathode: H2O H+ + OH-
2H+ + 2e- H2
H2O + O2 + 2e- 2OH-
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+ + 2e- H2
Therefore, hydrogen evolution type corrosion is simply the
displacement of hydrogen ions from the solution by metal
ions
 Acid waste

H Steel tank
2
Fe2+ H+ Fe2+
H+

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
 crack Drop of water

cathode
rust
rust
Film or scale
Fe2+ Fe2+

e- e-

Steel plate 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 Fe2+ + 2e-
At 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 + 2e- 2OH-
Fe2+ 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.