FORMS (TYPES)

OF
CORROSION:

Metals Environments- Conditions
The Eight Forms of Corrosion
1. General corrosion or uniform attack
2. Galvanic corrosion
3. Crevice corrosion
4. Pitting
5. Intergranular attack
6. Selective leaching or dealloying
7. Stress corrosion cracking
8. Erosion or velocity-accelerated
corrosion



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EVIRONMENTS

1) Dry atmosphere.
2) Damp (humid) atmosphere.
3) Wet atmosphere (rain, snow) .
4) Acids (HCl, HCIO
4
, H
3
PO
4
). RUSTING
5) Atmospheric contaminants.
6) Process water containing hydrogen sulfide
7) Brine solutions.
8) Industrial atmosphere.
9) Hydrocarbon containing wet hydrogen sulfide

In atmospheric corrosion which also exemplifies uniform
corrosion, a very thin layer of electrolyte is present. It is
probably best demonstrated by putting a small drop of
seawater on a piece of steel.

On comparing the atmospheric corrosion with aqueous
corrosion, the following differences are observed:

On a metal surface exposed to atmosphere, only a limited
quantity of water and dissolved ions are present, whereas the
access to oxygen present in the air is unlimited.

Corrosion products are formed close to the metal surface, unlike
the case in aqueous corrosion, and they may prevent further
corrosion by acting as a physical barrier between the metal
surface and environment, particularly if they are insoluble as in
the case of copper or lead.

The following is a simplified mechanism of aqueous corrosion of iron
(Fig. 4.2):


Mechanism of General Corrosion
Figure 4.2 Aqueous corrosion of iron
EXAMPLES OF UNIFORM CORROSION
Tarnishing of silver ware.
Tarnishing of electrical contacts.
Rusting of steels in open air.
Corrosion of offshore drilling platforms.
Corrosion of galvanized steel stairways.
Failure of distillation columns.
Corrosion of electronic components.
Corrosion of underground pipes.
Corrosion of automobile bodies.
Corrosion of heat exchanger tubes.
Corrosion of structural steels.

Prevention of Uniform Corrosion
Galvanizing (zinc coating)
Painting
Electroplating
Cathodic protection

2.-8. LOCALIZED CORROSION
A range of corrosion processes

Selective attack (part of surface), not all

Environment (CO
2
, Cl
-
, pH, Flow rate)

Material: Occurs at heterogeneous site of the metal
(segregation, inclusions, different phases, grain
boundaries).. i.e. structure non-uniformity or
discontinuity.

Mechanical
Stress (static or fluctuating)
2. Galvanic Corrosion
Occur when two different metals are in electrical
contact
Noble metal provides sites for cathodic reaction
Less noble metal act as the anode
Important factors in galvanic corrosion

a) relative areas of anode and cathode
b) difference in potential between anode and
cathode
c) effect of anodic polarization on anode (some
may passivate)

Important Parameters to consider:
Relative areas of anode and cathode.
At I
corr
: I
a
=I
c
, A
a
i
a
=A
c
i
c

Difference in potential between anode and cathode
EMF and Galvanic series

Anode may passivate

Effects of environment (e.g. electrolyte temp.)
Zinc and steel (inversion of anode and cathode at 100C)

Distance effects
Depends on the conductivity of the solution
MECHANISM OF GALVANIC CORROSION

Consider Fig. 4.4. For the formation of a galvanic cell (Fe and Cu),
the following components are required:

A cathode.
An anode.
An electrolyte.
A metallic path for the electron current.

In the case of copper and steel, copper has a more positive potential
according to the emf series, hence, it acts as a cathode.

On the other hand, iron has a negative potential in the emf series
(-0.44V), hence, it is the anode. As a matter of principle, in a
galvanic cell, the more noble metal always becomes the cathode
and the less noble always the anode.

Moisture acts as an electrolyte and the metal surface provides a
metallic path for the electron current to travel. Thus, when a piece of
copper is joined to iron, all qualifications required for the formation of
a galvanic cell are fulfilled and galvanic corrosion proceeds.

FACTORS AFFECTING GALVANIC CORROSION

The following factors significantly affect the magnitude of galvanic
corrosion:

1. Position of metals in the galvanic series.
2. The nature of the environment.
3. Area, distance and geometric effects.

1. Position of Metals in the Galvanic Series

As mentioned earlier, the further apart the metals are in the
galvanic series, the greater is the chance for galvanic corrosion.
The magnitude of galvanic corrosion primarily depends on how
much potential difference exists between two metals. For a
particular environment, the metals selected should be close to each
other in the galvanic series to minimize galvanic corrosion. Active
metals should not be joined with passive metals. Thus, aluminum
should not be joined to steel, as aluminum being more active would
tend to corrode.



2. The Nature of Environment

Due consideration must be given to the environment that surrounds
the metal.

- For instance, water containing copper ions, like seawater, is likely
to form galvanic cells on a steel surface of the tank.

- If the water in contact with steel is either acidic or contains salt, the
galvanic reaction is accelerated because of the increased ionization
of the electrolyte.

- In marine environments, galvanic corrosion may be accelerated
due to increased conductivity of the electrolyte.

- In cold climates, galvanic corrosion of buried material is reduced
because of the increased resistivity of soil.

- In warm climates, on the other hand, it is the reverse because of
the decreased resistivity of the soil
3. Area, Distance and Geometric Effects

The anode to cathode area ratio is extremely important as the
magnitude of galvanic corrosion is seriously affected by it. The area
ratio can be unfavourable as well as favourable.

The area ratio of the anode to cathode plays a dominant role in
galvanic corrosion. As a given amount of current flows in a galvanic
couple, the current density at the anode or cathode controls the rate
of corrosion.

For a given amount of current, the metal with the smallest area has
the largest current density and, hence, is more damaged if corrosion
occurs at it.

In Figure 4.6, the current density on aluminum bolt is very large
(small area) and serious galvanic corrosion of aluminum takes
place. This shows the end result of an unfavourable anode/cathode
ratio.



EXAMPLE OF GALVANIC CORROSION

Galvanic corrosion of aluminum shielding in buried
telephone cables.
Galvanic corrosion of steel pipe with brass fittings.
Galvanic corrosion of the body of the ship in contact
with brass or bronze propellers.
Galvanic corrosion between the tubes and the tube
sheet in heat exchangers.
Aluminium conduit buried in steel reinforced concrete
Galvanic corrosion of steel coated with copper due to
the defects in copper coating.
Galvanic corrosion inside horizontal stabilizers in
aircrafts.

METHODS OF PREVENTION OF GALVANIC CORROSION

1) Select metals, close together, as close as possible, in the galvanic
series.

2) Do not have the area of the more active metal smaller than the area
of the less active metal.

3) If dissimilar metals are to be used, insulate them.

4) Use inhibitors in aqueous systems whenever applicable and
eliminate cathodic depolarizers.

5) Apply coatings with judgment. Do not coat the anodic member of the
couple as it would reduce the anodic area and severe attack
would occur at the inevitable defect points in the coating.

Therefore, if coating is to he done, coat the more noble of the
two metals in the couple which prevents electrons being
consumed in a cathodic reaction which is likely to be corrosion-
rate controlling.
METHODS OF PREVENTION OF GALVANIC CORROSION
6) Avoid joining materials by threaded joints.

7) Use a third metal active to both the metals in the couple

8) Sacrificial material, such as zinc or magnesium, may he introduced
into this assembly.

For instance, zinc anodes are used in cast-iron water boxes of
copper alloy water-cooled heat exchangers.

9) In designing the components, use replaceable parts so that only the
corroded parts could be replaced instead of the whole assembly.

Above all, understand materials compatibility which is the key to
control galvanic corrosion.


Galvanic corrosion in alloys
Galvanic corrosion can occur between different phases in an
alloy
This is especially important when one of the phases is much
more active as a cathode.
Examples:

Copper-containing precipitates in aluminium alloys:
initiate pitting corrosion
Fe and Cu impurities in commercial zinc:
cause a large increase in corrosion rate compared to pure
zinc
3. Crevice Corrosion
Intensive corrosion frequently occurs with crevices and
other shielded areas of metal surface exposed to
electrolyte.

Can occur even under non metallic contacts, e.g.
rubber gaskets

Differential aeration cell is developed due to depletion
of O
2
under crevice.

This phenomenon limits the use (particularly of steels)
in marine environment, chemical and petrochemical
industries.

Main example: the case of passive SS alloys.


CAUSES of CREVICE CORROSION

a) Presence of narrow spaces between metal-to-metal
or non-metal-to-metal components

b) Presence of cracks, cavities and other defects on
metals.

c) Deposition of bio-fouling organisms and slimes.

d) Deposition of dirt, mud, dust, etc.. on a metal surface.

e) Existence of voids, gaps and cavities between
adjoining surfaces.


MATERIALS AND ENVIRONMENT

Conventional steels, e.g. SS 304 and SS
316, can be subject to crevice corrosion
in chloride containing environments,
such as brackish water and seawater.

Water chemistry plays a very important
role.


Joints
MECHANISM OF CREVICE CORROSION
A unified mechanism which is rather over-simplified is given
below (Fig. 4.17):





The four stages of crevice corrosion suggested are shown in Fig. 4.18

(1) Depletion of oxygen in crevice due to consumption in the cathodic reaction.
(2) Increase of acidity in the pit by the process of hydrolysis.
(3) Breakdown of the passive film on the surface at a critical value of pH.
(4) Propagation of crevice corrosion with further hydrolysis and production of
acidity.


PREVENTION OF CREVICE CORROSION

1) Use welded joints in preference to bolted or riveted joints.

2) Seal crevices by using non-corrosive materials.

3) Eliminate or minimize crevice corrosion at the design stage.

4) Minimize contact between metals and plastic, fabrics and debris.

5) Avoid contact with hygroscopic materials.

6) Avoid sharp corners, edges and pockets where dirt or debris could
be collected.

7) Use alloys resistant to crevice corrosion, such as titanium or Inconel.
Increased Mo contents (up to 4.5%) in austenitic stainless steels
reduce the susceptibility to crevice corrosion.
8) Apply cathodic protection to stainless steels by connecting to
adjacent mild steel structure.

9) For better performance of steels in seawater, allow intermittent
exposure to air to allow the removal of protective films.

10) Use inhibiting paste, wherever possible.

11) Paint the cathodic surface (not the anode).

12) Remove deposits from time to time i.e. Clean!

13) Take precautions against microbial corrosion, which creates
crevices and is damaging to low Mo stainless steels



PREVENTION OF CREVICE CORROSION (Contd)
4. PITTING CORROSION

DEFINITION

It is a form of localized corrosion of a metal surface where
small areas corrode preferentially leading to the formation
of cavities or pits while the bulk of the surface remains un-
attacked.

Metals which form passive films, such as aluminium and
steels, are more susceptible to this form of corrosion.

It causes failure by penetration with only a small percent
weight-loss of the entire structure.

It is a major type of failure in chemical processing industry
(CPI). The destructive nature of pitting is illustrated by the
fact that usually the entire system must be replaced!
Pitting Corrosion
Localized corrosion selectively attacks an area of a
metal surface where there is:

A surface scratch
An emerging dislocation
A compositional heterogeneity

The result is the formation of a hole
One of the most insidious form of corrosion

Weight loss is very small but grave consequences
ENVIRONMENT

Generally, the most conducive environment for pitting is the
marine environment.

lons such as Cl
-
, Br
-
and I
-
, in appreciable concentrations
tend to cause pitting of steel. Thiosulfate ions also induce
pitting of steels.

Aluminum also pits in an environment that cause the pitting
of steel.

Oxidizing metal ions (e.g. cupric, ferric and mercuric) with
chloride cause severe pitting.

Presence of dust or dirt particles in water may also lead to
pitting corrosion in copper pipes transporting seawater.

M
n+
M
O
2 OH
-
O
2 OH
-
1- Inside the growing pit the hydrolysis of M
n+
lowers the pH and breaks
down the passive film. The cathodic oxygen reduction reaction continues
outside the pit.

2- The presence of chloride is important, as it allows a pH of about 1 to be
achieved (HCl is a strong acid, and does not associate) and the metal
chlorides are very soluble (e.g. FeCl
2
).

3- Other anions (e.g. OH
-
and SO
4
2-
) can inhibit pitting, either by buffering
the pH in the pit or by causing the precipitation of a salt film.
Mechanism
PREVENTION OF PITTING CORROSION

1) Use materials with appropriate alloying elements
designed to minimize pitting susceptibility, e.g.
molybdenum (Mo) in SS.

2) Provide a uniform surface through proper cleaning, heat
treating and surface finishing.

3) Reduce the concentration of aggressive species in the
test medium, particularly chlorides.

4) Use inhibitors to minimize the effect of pitting, wherever
possible.

5) Make the surface of the specimen smooth and shiny and
do not allow any impurities to deposit on the surface.


PREVENTION OF PITTING CORROSION (Contd)

6) Minimize the effect of external factors on those design
features that lead to the localized attack, such as the
presence of crevices, sharp corners, etc.

7) Apply cathodic protection, wherever possible.

8) Coat the metals to avoid the risk of pitting.

10) Add anions, such as OH
-
to chloride environment.

11) Operate at a lower temperature, if service conditions
permit.