CREVICE CORROSION

Intensive localized corrosion frequently

occurs within crevices and other
shielded areas on metal surfaces
exposed to corrosives.
This type of attack is usually
associated by essentially stagnant
conditions which are caused by holes,
gasket surfaces, lap joints, surface
deposits and crevices under bolt
heads, rivet heads and so on.
As a result, this form of corrosion is
called crevice corrosion or,
sometimes, deposit or gasket
corrosion.
Examples of deposits that may produce
crevice corrosion (or deposit attack) are
sand, dirt, corrosion products, and other
solids. The deposit acts as a shield and
creates a stagnant condition there under.
The deposit could also be a permeable
corrosion product.
Contact between metal and nonmetallic
surfaces can cause crevice corrosion.
A gasket, Wood, plastics, rubber, glass,
concrete, asbestos, wax, and fabrics are
examples of materials that can cause
this type of corrosion.
Because metal-ion and oxygen
concentration differences exist during
crevice corrosion, the term
concentration cell corrosion has been
used to describe this form of attack.
Problems with crevice corrosion are a
major reason why bolted connections
are seldom used in submerged
applications, although cathodic
protection to minimize crevice
corrosion is possible.
MECHANISM OF CREVICE CORROSION

Consider a riveted plate section of

Metal M (e.g., iron or steel)
immersed in aerated seawater
(pH 7).
The overall reaction involves the
dissolution of metal M and the
reduction of oxygen to hydroxide ions:

Oxidation M → M+ + e

Reduction O2 + 2H2O + 4e- → 4OH-

As the corrosion within the crevice
increases, the rate of oxygen reduction
on the adjacent surface also increases.
This cathodically protect the external
surfaces.
There is often a long incubation
period associated with crevice attack
(more than 6 months).
Metals or alloys that depend on oxide
films or passive layers for corrosion
resistance are particularly
susceptible to crevice corrosion.
These films are destroyed by
high concentrations of chloride or
hydrogen ions.
Optimum crevice corrosion resistance
will be achieved with an active-passive
metal possessing:
1) A narrow active-passive transition
2) A small critical current density
3) An large passive region
Good:
titanium and
high-nickel
alloys
(Hastelloy C)

Bad: Type
430 stainless
steel
COMBATING CREVICE CORROSION

1. Use welded joints instead of

riveted or bolted joints and
avoid Porosity.

2. Existing lap joints should be

welded, caulked, or soldered to
close the crevices.
3. Design vessels for complete drainage
and avoid sharp corners and stagnant
areas.

4. Inspect and clean deposits frequently.

5. Remove solids in suspension early in

the process or plant flow sheet, if
possible.
6. Remove wet packing materials
during long shutdown periods.

7. Provide uniform environment, if

possible, as in the case of
backfilling a pipeline trench.

8. Use "solid" or non-absorbent

gasket , such as Teflon ,
wherever possible.
CONCENTRATION-CELL CORROSION

Anode and cathode cells will form on a

metal surface because of differences in
a given metal.

Cells can also form because of

differences in the environment. These
are called concentration cells or
solution cells.
•If a perfectly homogeneous and pure
metal surface is exposed to an
environment that is not identical at all
points, anodic and cathodic areas may
form and result in corrosion.
Metal-Ion Cells

Metals in contact with more dilute

solution will become more anodic
(active).
Its potential or electrode potential
(volts) decreases in more
concentrated solutions.
Oxygen Cells

Areas low in oxygen are anodic to

areas high in oxygen content.
Concentration cells are usually
associated by essentially stagnant
conditions which are caused by
holes, gasket surfaces, lap joints,
surface deposits and crevices under
bolt heads, rivet heads and so on.
The deposit acts as a shield and creates a
stagnant condition there under. The deposit
could also be a permeable corrosion product.

In active-passive metals (st.st.), low oxygen

causes active (anodic) areas to develop, such
as under a bolt head, where as the
surrounding metal remains passive or
cathodic. Thus an active-passive cell is set up
and corrosion occurs
PITTING
Pitting Corrosion
Pitting corrosion is perhaps the
most common form of oilfield
after general attack.

Pitting corrosion may start and

propagate quickly in relatively
short time periods, leading to
significant damage.
 Localized Corrosion - A good example showing
particulate deposits settling along the pipe bottom to
produce deep under deposit pitting. Testing showed
the side walls of the pipe near factory specification,
but total penetration of the pipe at the bottom and
lower sides.
It is a form of extremely localized
attack that results in holes in the
metal.

When the anode, or anodic area,

remains in one spot, corrosion
occurs at this site and deep
penetration results.
A lack of homogeneity at the metal-
corrosive interface, forming a local
cell.

Example: iron oxide, Fe3O4 on steel

formed at elevated temperatures. This
scale is noble to the steel and can
cause localized corrosion or pitting.
A local break through of the passive
film on the metal (such as st.st. Al,
Ni, Cr) results in a small anodic
sites.

Concentration cells due to deposits

are also the cause of pitting.
Most pitting failures are caused by the
chloride ion, particularly in stainless
steel. The chloride ion is characterized
by a "penetrating power" and tends to
break through passive surfaces.
Cupric and ferric chloride (CuCl2 and
FeCl3) are particularly bad pitting
agents for the stainless steels.

Seawater is a good example of a

chloride environment to which a
large amount of metal equipment is
exposed.
Pitting of 18-8 stainless steel by sulfuric
acid containing ferric chloride.
Note the sharply defined holes and the
lake of attack on most of the metal
surface.

Pits usually grow in the direction of

gravity.

Pits usually requires an extended

period before visible pits appear
(months to years), depending on both
the metal and the corrosive.
Once started, a pit penetrates the
metal at an ever-increasing rate.

Pits tend to undercut the surface

as they grow.

Pitting may be considered as the

intermediate stage between
general overall corrosion and
complete corrosion resistance.
Three identical specimens of 18-8
stainless steel to ferric chloride and
increasing the concentration and/or
temperature as we move to the right.
Mechanism of Pitting

A metal is being pitted by an aerated

sodium chloride solution.
Rapid dissolution occurs within the
pit, while oxygen reduction takes
place on the adjacent surface.
This process is self-stimulating and
self-propagating (auto catalytic
process).

The rapid dissolution of metal within

the pit tends to produce an excess of
positive charge in this area.
Migration of chloride ions to maintain
electron neutrality.

High concentration of MCl in the pit.

As a result of hydrolysis, high

concentration of hydrogen ions are
present in the pit.
Both hydrogen and chloride ions
stimulate the dissolution of most metals
and alloys .

Since oxygen solubility in concentrated

solutions is virtually zero, no oxygen
reduction occurs within a pit.
Solution Composition
CuCl2 and FeCl2 do not require the
presence of oxygen to promote attack
because their cations can be
cathodically reduced.

Halides of non oxidizing metal ions

(NaCl, CaCl2) cause pitting but to a
much lesser degree of
aggressiveness.
Fluorides and iodides have
comparatively little pitting tendencies.

Pitting can be prevented or reduced in

many instances by the presence of
hydroxide, chromate, or silicate salts.

These substances tend to accelerate

pitting when present in small
concentrations.
Velocity
Three identical 316 stainless steel
pieces in acid-ferric chloride mixture
at elevated temperature, for 18 hours.

Pitting is usually associated with

stagnant conditions such as a liquid
in a tank.
Increasing velocity, often decreases
pitting attack.
Metallurgical Variables

Stainless steel alloys are more

susceptible to damage by pitting
corrosion than are any other group of
metals or alloys.
Surface finish often has a marked effect
on pitting resistance (polished or rough
surface).

Holding type 304 and 316 stainless

steel in sensitizing temperature range
(950-1450 °F) decreases their pitting
resistance.

Austenitic stainless steels exhibit the

greatest pitting resistance when
solution quenched above 1800 °F.
Several cold-working increases the
pitting attack of 18-8 stainless steels in
ferric chloride.
Pitting is usually associated with
stagnant conditions such as a liquid in a
tank or a deposit in a pipe handling
flowing material.
Velocity or increasing velocity often
decreases pitting attack.

For example, a stainless steel pump

would give good service handling
seawater if it were run "around the
clock" but would pit if the pump shut
down (and remained full of water).
COMBATING PITTING

1. Same as concentration cell corrosion

(cathodic protection, protective
coatings, and corrosion inhibitors

2. Material selection: The addition of 2%

Mo to 18-8 stainless to produce Type
316 stainless results in a very large
increase in resistance to pitting.
Titanium alloys are generally
considered to be immune to
pitting corrosion, but palladium or
molybdenum additions are found
to be helpful in adding resistance
at elevated temperatures.