CORROSION ENGINEERING

PITTING AND CREVICE

CORRSION
ALFORQUE, DANYLLE ADRIENNE J.
 PITTING CORROSION
It is a form of localized corrosion of a metal surface where
small areas corrode preferentially leading to the formation of
cavities or pits, and the bulk of the surface remains unattacked.
It is a major type of failure in chemical processing industry. The
destructive nature of pitting is illustrated by the fact that
usually the entire system must be replaced.

It is the most insidious form of corrosion.

CRITICAL PITTING POTENTIAL OF
PITTING CORROSION
SURFACE DEFECTS
Such as inclusions, second phases and
surface heterogeneity, have been
identified with initiation of pits. It has
been established that sulfide inclusions
are mainly responsible for pitting of
carbon and stainless steels.
SENSITIZING
TEMPERATURE
The temperature zone which
promotes intergranular corrosion of
steels also promotes pitting, because
of the weakening of grain
boundaries.
SURFACE FINISH DEGREE OF COLD WORK
A smooth surface does not allow Severe cold working increases pitting
accumulation of impurities and stagnancy to susceptibility as shown by austenitic
build up on the metallic surface, thus steels in ferric chloride solution.
minimizing the risk for the formation of
differential aeration cells and minimizing
corrosion and pitting. However, the pits
which are formed on a smooth and shiny
surface are deeper and larger compared to a
rough surface.
VELOCITY
It is a matter of common observation that a
stainless steel pump handling seawater
gives a good service if it is used to run
continuously, but it would tend to pit if
stopped because of the formation of
differential aeration cells. Pits are often
associated with stagnant conditions. High
velocity may cause passivation of the steel
surface by greater control of the oxygen with
the steel surface, thus enabling the integrity
of the passive film to be maintained.
ENVIRONMENTAL
CONTAMINATION
An environment contaminated by dust
particles would be more conducive to
pitting. Dust particles on metals
absorb moisture and lead to the
formation of differential aeration cells.
Salt particles in a marine environment
when deposited on a metal surface
lead to intensive pitting of equipment
and appliances.
MECHANISM OF PITTING CORROSION
In order for pitting to take place, the formation of an anode is a prerequisite. With the formation of
an anode, a local corrosion cell is developed. The anode may be formed as a result of

a) lack of homogeneity at the metal b) destruction of a passive film. The

corrosive interface. Lack of homogeneity
on the metal surface is caused by
impurities, grain boundaries, niches, rough
surface, etc. The difference in the
environments can cause, for instance, the
formation of concentration cells on the
metal surface
lack of homogeneity at the metal corrosive interface. Lack of homogeneity
on the metal surface is caused by impurities, grain boundaries, niches,
c) deposit of debris or solids on the metal
rough surface, etc. The difference in the environments can cause, for
instance, the formation of concentration cells on the metal surface
surface. This generally leads to the
formation of anodic and cathodic sites
destruction of a passive film results in the
formation of a small anode. Therefore, a
breakthrough of the protective film on the
metal surface results in several anodic sites
and the surrounding surface acts as a
cathode. Thus, an unfavorable area ratio
results
d) formation of an active–passive cell with a
large potential difference. The formation of a
small anode on the passive steel surface, for
instance, leads to the formation of the above
cell.
 EVALUATION OF PITTING
CORROSION
The development of pit depths
Conventional weight-loss techniques cannot be follows a time function:
used to evaluate pitting because of its localized D = Ktc
nature. What matters in pitting is the depth of the
where
deepest pit, which is an indicator of the
D = depth of the deepest pit
resistance of a material to pitting. Although the
depth is related to the sample size, it is often
K= alloy surface area and
used as a criteria of pitting resistance in environment-dependent constant
laboratory tests. The prediction should always be t= time and
made on a combination of results obtained from c= environment-dependent
number of pits per mm2 and average pit depth. parameter often close to a
EFFECT OF TEMPERATURE
This relationship is, however, differs for other grades of
steels. Generally a rise in temperature shifts the critical
pitting potential (Ep) in the more active direction, which
leads to acceleration of pitting. Critical pitting potential (Ep)
is synonymous with the breakdown potential (Eb). There is a
critical pitting temperature below which pitting will not
occur.
 EFFECT OF ALLOY
COMPOSITION
The effect of certain alloying elements on the breakdown potential
is important. Generally, the alloying elements which have a
beneficial effect shift Ep to a more positive value, whereas the
elements having detrimental effects shift Ep to more negative
value. Generally, Mo, Cr, Ni, V, Si, N, Ag and Re improve pitting
resistance of stainless steels.
 Pitting corrosion occurs at small discrete locations on the
metal surface and penetrates the metal 20-100 times faster
than general corrosion. This leads to much earlier failure of
metallic equipment than if just general corrosion were
present.

Although organic inhibitors have been widely used to inhibit

general corrosion, with the hope that they would also reduce
pitting corrosion, it is conventionally believed that pitting
corrosion could not be effectively inhibited in highly

INHIBITION
oxygenated systems without employing heavy metals such
as Zn or Cr.

OF PITTING
It was discovered that pitting corrosion can be effectively
inhibited without heavy metals such as Zn or Cr and can be
effectively inhibited with organic inhibitors even in the
absence of An or Cr.
CORROSION It was further discovered that certain synergistic mixtures of
organic inhibitors effectively inhibit pitting corrosion,
particularly where the mixture of organic inhibition is a blend
of both anodic and cathodic organic inhibitors.
CREVICE CORROSION
This is a localized form of corrosion, caused by the
deposition of dirt, dust, mud and deposits on a metallic
surface or by the existence of voids, gaps and cavities
between adjoining surfaces. An important condition is
the formation of a differential aeration cell for crevice
corrosion to occur. This phenomenon limits the use,
particularly of steels, in marine environment, chemical
and petrochemical industries.
EFFECT OF TEMPERATURE
The rate of crevice corrosion propagation of stainless steel
alloys, such as types 304 and 316, is decreased in natural
seawater, when the temperature is increased from ambient to
◦
70 C [8,9]. The tendency for initiation of crevice corrosion is not
affected by increase in temperature. The above trend may be
attributed to the decreased solubility of oxygen with increased
temperature and changes in the nature of the passive film which
is formed.
 FILIFORM CORROSION
Filiform corrosion is a special case of crevice corrosion. During propagation,
water is supplied to the head of the filament from the surrounding
atmosphere by osmotic action due to the high concentration of dissolved
ferrous ions on the surface of steel substrate.

Filiform corrosion is a form of corrosion that occurs under some thin

coatings in the form of randomly distributed threadlike filaments. It is also
known as "underfilm corrosion" or "filamentary corrosion".
 PREVENTION OFCREVICE
CORROSION
Use welded joints in preference to bolted or Avoid contact with hygroscopic materials.
riveted joints.

Avoid sharp corners, edges and pockets where

Seal crevices by using non-corrosive materials. dirt or debris could be collected.

Eliminate or minimize crevice corrosion at the In critical areas, use weld overlays with highly
design stage corrosion resistant alloy.

Minimize contact between metals and plastic, Use alloys resistant to crevice corrosion, such
fabrics and debris. as titanium or Inconel.
 PREVENTION OFCREVICE
CORROSION
Apply cathodic protection to stainless steels by Use inhibiting paste, wherever possible.
connecting to adjacent mild steelstructure.

Paint the cathodic surface.

Take precautions against microbial corrosion,
which creates crevices and is very damaging to
low Mo stainless steels.
Remove deposits from time to time.

For better performance of steels in seawater,

allow intermittent exposure to air to allow the For seawater service, maintain a high velocity to
removal of protective films. keep the solids in suspension