3.

PIT TING C ORR OS ION

( K a k i s a n B o p e n g / Pe m b o p e n g a n )

Pitting corrosionon outside

surface of cast iron bathtub.

Source:
http://www.metallurgist.com/images/Corrosion/Corrosion2.jpg

Pitting corrosion on the

bottom of a tank.

Source: http://www.forensic.cc/images/00210m.jpg

3.4 PITTING CORROSION

DEFINITION
Pitting corrosion is a
localized corrosion that
may either be shallow
or deep but is often
difficult to identify. By
the time pitting
corrosion is visible to
humans, the damage
is often extensive

3.4 PITTING CORROSION

DEFINITION
A form of extremely localized
attack that results in holes or
pits or cavity (small or large in
diameter) in metal.
Pits are sometimes isolated or
so close toghether that they
look like a rough surface
Note:
The most destructive and
insidious forms of corrosion due to
its nature and difficulties to
measure it quantitatively.

3.4 PITTING CORROSION

DEFINITION
Pitting corrosion occurs in materials that have a
protective film such as a corrosion product or
when a coating breaks down.
The exposed metal gives up electrons easily and
the reaction initiates tiny pits with localised
chemistry supporting rapid attack
Note:
Pits can be crack initiators in stressed components or
those with residual stresses resulting from forming
operations. This can lead to stress corrosion cracking

3.4 Pitting Corrosion

EXAMPLES

Pitting corrosion of a stainless steel pipe, showing

growth of pits under the metal surface.
Source: R. Newman Pitting (2010) Corrosion of Metals, The Electrochemical Society Interface

3.4 Pitting Corrosion

MECHANISM
It occurs inside small holes
(pits) on the surface of a
metal's passive oxide or
hydroxide layer, which is
attacked locally by, among
other species, chloride ions.

Increasing the chloride ion

concentration, increasing the
temperature, and decreasing
the pH will all contribute to
an increased rate of corrosion

3.4 Pitting Corrosion

MECHANISM: THE
STAGES

P I T I N I T I AT I O N .
An initial pit may form on the surface covered by a
passive oxide film as a result of the following:
Mechanical damage of the passive film caused by scratches.
Anodic reaction starts on the metal surface exposed to the
electrolyte. The passivated surrounding surface act as the
cathode.
Particles of a second phase (non-metallic inclusions,
intermetallic inclusions, metallic particles, Microsegregation)
emerging on the metal surface. These particles precipitating
along the grains boundaries may function as local anodes
causing localized galvanic corrosion and formation of initial pits.
Localized stresses in form of dislocations emerging on the
surface may become anodes and initiate pits.
Non-homogeneous environment may dissolve the passive film at
certain locations where initial pits form.

3.4 Pitting Corrosion

MECHANISM: THE
STAGES
PIT GROWTH
In presence of chloride ions pits
are growing by autocatalytic
mechanism (refer figure).
Anodic reactions inside the pit:

Fe Fe2+ + 2e- (dissolution of

iron)
The electrons given up by the
anode flow to the cathode
(passivated surface) where
they are discharged in the
cathodic reaction:

O2 + H2O + 2e- 2(OH-)

3.4 Pitting Corrosion

MECHANISM: THE
STAGES
As a result of these reactions
the electrolyte enclosed in the
pit gains positive electrical
charge in contrast to the
electrolyte surrounding the
pit, which becomes negatively
charged.
The positively charged pit
attracts negative ions of
chlorine Cl- increasing acidity
of the electrolyte according to
the reaction:
FeCl2 + 2H2O = Fe(OH)2 + 2HCl

3.4 Pitting Corrosion

MECHANISM: THE
STAGES
pH of the electrolyte inside
the pit decreases (acidity
increases) from 6 to 2-3,
which causes further
acceleration of corrosion
process.
Large ratio between the
anode and cathode areas
favors increase of the
corrosion rate.
Corrosion products (Fe(OH)3)
form around the pit resulting
in further separation of its
electrolyte.

3.4 Pitting Corrosion

PREVENTIVE
MEASURES

Selection of appropriate material;

Providing stirring of the electrolyte;
Control of the electrolyte composition
(pH, chloride ions);
Corrosion inhibitors;
Cathodic protection;
Corrosion protection coatings.

3.4 Pitting Corrosion

END OF PITTING
CORROSION

After this INTERGRANULAR CORROSION