Experiment-7

Aim of the Experiment

Pit Density :
To find pit density along the given area of stainless steel
sample.

Theory:
Pitting corrosion, or pitting, is a form of localized corrosion
that leads to the creation of small holes in the metal. The
driving power for pitting corrosion is the depassivation of a
small area of the specimen, which becomes anodic while an
unknown but potentially vast area becomes cathodic, leading to
very localized galvanic corrosion. The corrosion penetrates the
mass of the metal, with limited diffusion of ions. The
mechanism of pitting corrosion is probably the same as crevice
corrosion.
Mechanism
Pitting can be separated into two different regions, namely pit
initiation and pit growth. The growth mechanism is reasonably
well understood, while initiation mechanism is not very clear.
Pit Initiation
Pit initiation is not well understood. Pit initiation time can vary
from very short, days, to very long times, many years. Small
changes in conditions can make the difference in whether pits
occur or not.
There are many mechanisms of pit initiation. The initiation
mechanism could be metal specific and history dependent in
some cases. In other situations a general type of pit initiation
mechanism may be invoked. Most mechanisms involve a
breakdown of the passive layer on a metal. The passive layer is
thought to be a complicated layer on the surface of a metal. It

is a layer which is 30 to 100 Angstroms thick. As an atom is

only about 2 Angstroms in diameter, then a passive layer is
only about 15 to 50 atoms thick. Experimentally this is very
difficult to examine, especially in pitting investigations when
the experimentalist does not know which site is going to pit.
The passive layer is thought to be a two phase type of structure
with the side nearest the metal a crystalline phase while the
layer nearest the solution side is thought to be an amorphous
mixture of metal ions and hydroxyl ions.
Initiation Mechanisms
1. Defect Theory.
Early investigators suspected that defects in the film broke
down. The film defects were related to metal defects such as
grain boundaries or slip steps due to dislocations emerging
form the surfaces. These sites would be local anodes and
initiate breakdown as the film probably was not fully formed
over these local anomalies. Unfortunately, although some
materials show a relationship between pits and defects, it is not
a general rule.
2. Chloride Ion Dissolution.
Many metal chlorides are soluble in water. One theory used this
fact to suggest that at the solution/passive layer interface the
chloride ion replaced the hydroxyl ion to form a metal chloride
that dissolved. Another chloride ion at the same location then
dissolved some more of the passive layer until the bare metal
was exposed. Further chloride ion dissolution would then form a
pit into the metal. This mechanism predicts that once a pit
forms it will continue to grow. Unfortunately, some pits cease to
grow.
Pit Growth
From a mechanistic point of view, the growth of a pit can be
regarded as similar to the corrosion process in a crevice,

covered in the previous section. The exposed surface outside

the growing pit is cathodically protected by supporting the
reduction of oxygen to hydroxyl ion reaction:O2 + 2H2O + 4e- -> 4(OH-)
As this cathodically protects the region outside the pit, the
metal dissolution region cannot spread laterally across the
surface. In addition the large cathodic surface can maintain this
reaction and form a large cathode to small anode ratio which
will accelerate the anodic reaction.
Within the pit, which is regarded as a small hemisphere at this
stage, the metal dissolution reaction is taking place. This is the
general anodic reaction of:M ->Mz+ + zeHowever, it is the only reaction within the pit and results in an
electrical imbalance again which attracts negatively charge
ions, usually chloride ions. The autocatalytic reaction to form
hydrochloric acid in the pit is initiated and continues:Mn+ + Cl- + zH2O ->M(OH)z + z(H+Cl-)
Pitting, like crevice corrosion, is an autocatalytic reaction once
it is started and the pH decreases while chloride ion
concentration increases inside the pit.

Procedure:1.A stainless steel sample is taken and the surface of the

sample is thoroughly polished.
2. It is dipped in a solution containing 1 N H2SO4 and 0.3 N
NaCl for a designated time.
3. The surface is observed under the optical microscope and
the total number of pits on the surface are calculated.
4. The procedure is repeated with a similar sample for a
different time interval

Observations:Length of the sample- 2.4 cm.

Width of the sample- 0.3 cm.
Area= 0.75 cm2.
Time interval=5 seconds Total number of pits=122
Pit density = 163 pits/cm2
Time interval = 15 seconds
Total number of pits- 187.
Pit Density= 250 pits/cm2.
Time interval= 20 seconds Total number of pits= 225
Pit density=300 pits/cm2
Time interval = 30 seconds Total number of pits = 240
Pit density=320 pits/cm

Precautions:
1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax error.
3. The pit density doesnt increase after a specific time interval
as new pits stop forming and the initiated pits grow in depth.