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Corrosion contd.

Galvanic or contact corrosion

Contd.
Occurs when two dissimilar
metals are in electrical contact
with each other and are
exposed to an electrolyte
Severity of the corrosion of the
anodic metal depend upon the
relative position of the two
metals in the galvanic series

Contd.

Zn less noble readily dissolves forms anode


Cu more noble acts as cathode
Cathodic reaction may occur either by hydrogen evolution
process or by the oxygen absorption process depending on the
corrosive environment
Dissimilar metals in contact with each other corrosion is
rapid due to galvanic reaction
If direct contact between dissimilar metals can be avoided no
rapid corrosion of the anodic metal
Hence, fabrication of metals by riveting or welding should be
done with materials having the same chemical composition as
the base metal

High temperature corrosion


Known as oxidation different from wet

corrosion
Metals are widely used at high
temperatures therefore, behaviour of
metals at high temperature is of great
interest
High temperature oxide films and
scales are formed

Contd.
Corrosion like rusting of the ferrous
alloys are formed
Oxide films formed or some metals
act as diffusion barriers
Alloying elements like Cr, Al, Si etc.
get oxidized and concentrated in the
scale layer corrosion resistance
improves

passivity
Defined as a phenomenon in which a metal
or an alloy exhibits a much higher
corrosion resistance than its position in
the electrochemical series would indicate
Passive state less reactive
Ti, Cr, Al and stainless steel passive
metals

Reasons for passivity


Formation

of a highly protective, but


very thin and quite invisible film on the
surface of the metal
Films must be nonporous, insoluble
and self-healing when mechanically
damaged
Metal also becomes passive because
of a chemically absorbed layer of
oxygen on the metal surface

Contd.
This layer is only one molecule thick and
will be self-healing
Passivation applies only to certain
environmental conditions which tend to
maintain a protective oxide film on the
metal surface.

Factors influencing corrosion rate

Depending on metals:
1. Electrode potential of metal or its
position in the galvanic series (usually
anodic metals corrode faster)
2. Hydrogen over voltage (i.e. ease of
hydrogen evolution)
3. Chemical inhomogeneities, e.g.,
inclusions, impurities, different phases,
which promote the formation of anodic and
cathodic sites

Contd.
4. Physical inhomogeneities, i.e., regions
of high residual stress in the metal. This
region tend to become anodic with respect
to those regions which are free from stress
5. Passivity of the metal, i.e., formation of
thin films of oxide

Factors depending on
environment
1. pH of the solution; pH = 7 and
alkali solution less corrosive;
pH<7, more corosive
2. Nature & concn. Of other ions, and
the degree of agitation - excessive
agitation is detrimental because of
abrasion and breakage of the
protective film

Contd.
3. Influence of oxygen in the solution a
constant supply of oxygen is necessary for
corrosion to continue
4. Increase in temperature increases
ionization and fluidity of the solution and
the rate of reaction
5. Presence of stress due to mechanical
working increases corrosion of the
stressed zones due to potential difference
on the metal surface

Specific types of corrosion


1. Atmospheric corrosion
2. Underground corrosion
3. Microbial corrosion
4. Liquid metal corrosion
5. uniform corrosion
6. Pitting corrosion
7. Crevice corrosion
8. Intergranular corrosion
9. Fretting and selective corrosion
10. Stress corrosion
11. Corrosion fatigue
12. Erosion corrosion

1. Atmospheric corrosion
Primarily due to the combined effects of film formation

and film breakdown


Rate of atmospheric corrosion depends up on (i)
nature of metal (ii) degree of protection offered by the
film present or produced (iii) nature of the electrolyte
present
Cracks and discontinuities in the film produced
expose fresh areas of the metal to humid atmosphere
localized corrosion cells are formed
Because of these cells, local corrosion current flows
between the anodic areas of freshly exposed metal
and the large cathodic areas of the coated metal
Hence, mechanism of atmospheric corrosion is
oxygen absorption mechanism

Contd.
Electrolyte usually rain water and humid
atmosphere; dissolved gases such as CO2
or SO2 increases the acidity of the
atmospheric moisture
Rain supplies the moisture necessary for
electrochemcial attack; washes a large
part of the film from a metal surface; the
surface is exposed for the attack
Atmospheric corrosion is severe on ferrous
metals, while non-ferrous metals form dull
surfaces in the presence of natural
environment

2. Underground corrosion
Also

known as soil corrosion


Depends up on the corrosive nature of the
soil; causes serious damage to materials
Corrosive properties of soil depend on their
acidity, degree of soil aeration, electrical
conductivity, salt and moisture content
Bacteria and micro-organisms in the soil can
also greatly enhance the rate of corrosion

Contd.
In underground soil corrosion, galvanic
corrosion arising from contact between
different metals happens frequently
Ex : Cu pipe service line connected to a cast
iron main, galvanic cell is formed
Ground rod of bare Cu connected to a steel
piping, galvanic corrosion cell is formed
Concentration cells are responsible for much
of the corrosion taking place in the soil

Contd.
Pipelines pass through different
soils; when two different soils are in
contact with a single piece of metal,
concentration cell is formed
That portion of the pipe lying in more
concentrated soil is the anode and
that in less concentrated cell is the
cathode
Moisture acts as the electrolyte,
pipe itself furnishes the connecting
circuit

Contd.
Oxygen

concentration cells are very common


on buried pipe
Temperature cell is another kind; e.g. gas
transmission cell laid in soil ; hot compressed
gas makes the pipe near the compressor
anode and the copper pipe down in th line is
the cathode
In acid soils, corrosion mechanism is similar
to that of the hydrogen evolution type

Microbial corrosion

This is caused by the metabolic activity of various micro


organisms
More important micro-organisms responsible for most
corrosion are:
(i) sulphate reducing bacteria
(ii) sulphur bacteria
(iii) Iron and manganese bacteria
(iv) micro-organisms capable of forming microbiological
films
Metal pipes and structures buried in the damp soil
containing sulphates and organic matter are attacked by
the sulphate reducing bacteria
The corrosion product is iron sulphide instead of rust
Bacteria attack is fast and localized

Contd.
The corrosion product is iron sulphide
instead of rust
Bacteria attack is fast and localized

4. Liquid metal corrosion


Liquid metals produce unusual types of
deterioration in the materials which they come in
contact during operation like steel making, metal
casting or heat transfer using liquid metals
Mechanism not electrochemical; no transfer of
electrons
Instead processes involved are:
solution of solid material
formation of chemical compounds
diffusion of liquid metal into the solid material

Contd.
Occurs in devices for nuclear power
Here, corrosion (essentially a process of mass transfer) is not
dependent upon local cell local cell potentials for its driving force
Corrosion occurs by simple dissolution of the reactor components at
the high temperature
In the heat exchanger the liquid metal temperature drops solubility
of the metal in the coolant liquid metal is lowered and is deposited
on the surface
Thus hot zones are continuously thinned and the heat exchanger
tubes are clogged resulting in frequent shut down
Usually inhibitors are added in to the liquid metal to slow down such
a corrosion

5. Uniform corrosion
Uniform

over a given surface,


relatively superficial and unlocalized
Unlocalized attack may start in its
initial phase at certain areas and
spreads over the whole surface the
metal gradually
Therefore, whole surface is
uniformly corroded in course of time

6. Pitting corrosion
Serious type of localized corrosion through

the electrochemical reaction


Occurs when protective films generally
continues and then break down in some
environment producing cell action
Point of film breakage becomes anode while
the surrounding unbroken film acts as
cathode small galvanic cells are created
producing pits

Contd.
Corrosion products may form caps over pit
cavities
Shapes of the pits vary widely usually
these are saucer shaped, conical or
hemispherical
Only a small amount of metal is corroded
but perforations or holes that are
developed can lead to costly repair of
expensive equipment
Pitting causes more unexpected corrosion
loss than other types of corrosion

7. Crevice corrosion

Occurs in cracks or crevices formed between


mating surface of metal assemblies and
takes the form of pitting or etched patches
Localized form of corrosion
Both surfaces may be of the same metal or
of dissimilar metals or one surface may be a
non-metal
Can also occur under scale and surface
deposits and under loose fitting washers and
gaskets

Contd.
Crevice corrosion results as a result of
differential aeration cell
Occurs only at film protected metals
such as Al, Mg, stainless steel and
titanium

8. Intergranular corrosion
A form of localized surface attack in which
a narrow path is corroded out
preferentially along the grain boundaries
of a metal
Driving force is the difference in corrosion
potential that develops between a thin
grain boundary zone and the bulk of the
immediate adjacent grains
The constituent may be anodic, cathodic
or neutral to the base metal or adjacent
zone

Contd.
Example for anodic constituents are Mg5Al8,
MgZn2 in Al alloys and Fe4N in iron alloys
Examples for cathodic constituents are
FeAl3 and CuAl2 in Al alloys and Fe3C in iron
alloys
If the precipitate is anodic to the adjacent
zone, precipitate corrodes preferentially
and if the precipitate is cathodic, the
adjacent zone is corroded
Occurs most commonly in Al, Cu and 18/8
stainless steel (18% Cr, 8% Ni)

9. Fretting and selective corrosion


Fretting corrosion is local surface
discolorations and deep pits
Selective corrosion another type of
localized corrosion
Most common example is
dezincificaion of brass
Occurs in soft water

10. Stress corrosion


Combination of tensile stress and corrosive

environment
One of the causes of failures of metal structure
Known as stress corrosion cracking
Stress may be residual or applied
It may be low enough and will cause no concern in
the absence of the environment
Stress corrosion cracking usually occurs under only
very mild corrosive conditions
No metal loss or general corrosion associated with it

Contd.
Cracks may be intergranular, trans granular or a

combination of both
Occurrence and rate of stress corrosion are
influenced by stress level, corrosive agent, time and
temperature of exposure, structure of the metal,
amount of plastic strain, behavior of protective films
etc.
Usually found in Al alloys, low carbon steels and
brass
Occurs on mild steel exposed to alkaline solution at
high temperature and stresses

11.Corrosion fatigue
Involves

the reduction in the fatigue strength


of a metal
Due to combined action of fatigue and
corrosion
When a metal is subjected to cyclic stress,
number of cycles required to cause failures at
a given stress will be reduced in a corrosion
environment
Attacks existing surface flaws such as cracks
or forms new intergranular cracks

12. Erosion corrosion


Refers to acceleration of corrosion by
simultaneous abrasion by the turbulent flow of
gases or liquids
Caused by the breakdown of a protective film at
the place of impingement and its subsequent
inability to repair itself under existing conditions
Removes protective films from localized areas in
the metal surface, thereby contributes to the
formation of differential cells at such areas and
localized pitting takes place at the anodic points
of the cells
Most commonly found in condenser tubes, piping,
agitator and vessels in which stream of liquid
emerge from a pipe and strike a wall of the vessel