CHAPTER 3

FORMS OF CORROSION

Chapter Outlines
3.1
3.2
3.3
3.4

Galvanic or Two-Metal Corrosion

Crevice Corrosion
Pitting Corrosion
Intergranular Corrosion
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GALVANIC CORROSIO

3.1 Galvanic or Two-Metal Corrosion

also called ' dissimilar metal corrosion.
Takes place when two metals are in physical contact with each other
and are immersed in a conducting fluid.
corrosion damage induced when two dissimilar materials are coupled in
a corrosive electrolyte.
Examples:
1. Plate and screw of different electrical potentials due to
differences in processing
2. Multiple component implant using different metals for each
component
3. Copper and steel tubing are joined in a domestic water heater,
the steel will corrode in the vicinity of the junction
The following fundamental requirements have to be met for
galvanic corrosion:
1. Dissimilar metals (or other conductors, such a graphite).
2. Electrical contact between the dissimilar conducting materials
(can be direct contact or a secondary connection such as a
common grounding path).
3. Electrolyte (the corrosive medium) in contact with the
dissimilar conducting materials.

The relative nobility of a material can be predicted by

measuring its corrosion potential. The well known
galvanic series lists the relative nobility of certain
materials in sea water. A small anode/cathode area ratio
is highly undesirable. In this case, the galvanic current is
concentrated onto a small anodic area. Rapid thickness
loss of the dissolving anode tends to occur under these
conditions. Galvanic corrosion problems should be solved
by designing to avoid these problems in the first place.

Fig. Galvanic corrosion between

stainless steel screw and
Aluminium.

Fig. Galvanic corrosion between

Steel and Brass.

Noble, cathodic end

Platinum
Gold
Graphite
Titanium
Silver
Hastelloy C
18-8 austenitic stainless steels (passive condition)
Iron-chromium alloys (passive condition)
Inconel (passive)
Nickel
Monel
Cupronickel alloys
Bronzes
Copper
Brasses
Inconel (active)
Nickel (active)
Tin
Lead
18-8 Austenitic stainless steels (active)
13% Chromium stainless steel (active)
Cast iron
Mild steel and iron
Cadmium
Aluminum alloys
Zinc
Magnesium and magnesium alloys
Active, anodic end

Fig. Anodic- cathodic behavior of steel

with zinc and tin outside layers exposed to
the Atmosphere.
(a) zinc is anodic to steel and corrodes
(b) steel is anodic to tin and corrodes (the
tin layer was perforated before the 4
corrosion began)

The following have been described as " main

factors"
factors influencing galvanic corrosion rates in
Skanaluminium's on-line publication "Alubook Lexical knowledge about aluminium".
Potential Difference between materials
Cathode Efficiency
Surface areas of connected materials (area
ratio)
Electrical resistance of the connection between
the materials and of the electrolyte.

Note that the area ratio of the anode:

cathode is an important variable affecting
the dissolution current density (and hence
corrosion rate) pertaining to the anode.
The area ratio is also important when
considering the relative amount of current
"available" from the cathodic reaction.

Fig. Brass on Weathering Steel - rust forms in

discrete crystallites that are fine, red and diffusely
reflecting, like hematite. The massive re-crystallized
layer is a shiny blue, approaching the blue-black of 5
secular hematite.

CREVICE CORROSION

Rivets : a metal pin for passing through holes in two or more plates or pieces
to hold them together, usually made with a head at one end, the other end
being hammered into a head after insertion.
Depletion : to decrease seriously or exhaust the abundance or supply of

3.2 Crevice Corrosion

Crevice corrosion is a localized form of corrosion usually associated with a
stagnant solution on the micro-environmental level.
Such stagnant microenvironments tend to occur in crevices (shielded areas)
such as those formed under gaskets, washers, insulation material, fastener
heads, surface deposits, disbonded coatings, threads, lap joints and clamps.
Occurs under gaskets, rivets and bolts, between valve disks and seats.
Well-known examples of such geometries including flanges, gaskets, disbonded
linings/coatings, fasteners, lap joints and surface deposits.
Crevice corrosion is initiated by changes in local
chemistry within the crevice:

Depletion of inhibitor in the crevice

Depletion of oxygen in the crevice
A shift to acid conditions in the crevice
Build-up of aggressive ion species (e.g.
chloride) in the crevice
7

Mechanism- Chronology of Crevice Corrosion

Stage 1
At time zero, the oxygen
content in the water
occupying a crevice is
equal to the level of
soluble oxygen and is the
same everywhere.

Stage 2
Because of the difficult access
caused by the crevice
geometry, oxygen consumed
by normal uniform corrosion is
very soon depleted in the
crevice. The corrosion
reactions now specialize in
the crevice (anodic) and on
the open surface (cathodic).
Fig. Schematic illustration (initial stage) of the
mechanism for crevice corrosion between two riveted
Stage 3
sheets.
The crevice development a few more accelerating factors fully develop:
1. The metal ions produced by the anodic corrosion reaction readily hydrolyze giving off
protons (acid) and forming corrosion products. The pH in a crevice can reach very
acidic values, sometimes equivalent to pure acids.
2. The acidification of the local environment can produce a serious increase in the
corrosion rate of most metals. See, for example, how the corrosion of steel is affected
as a function of water pH.
8
3. The corrosion products seal even further the crevice environment.
4. The accumulation of positive charge in the crevice becomes a strong attractor to

Fig. Crevice corrosion on aircraft

Fig. Pack rust is a form a localized corrosion typical of

steel components that develop a crevice into an open
atmospheric environment. This expression is often used
in relation to bridge inspection to describe built-up
members of steel bridges which are showing signs of
rust packing between steel plates.

Zebra mussels- an example of marine environm

Close-up picture showing the severity9of corro

Underside of panel where severe corrosion was found

Crevice Corrosion Testing

ASTM G78
Standard Guide for Crevice Corrosion Testing
A good example of how crevice corrosion can be reproduced and accelerated in a laboratory environment
is the formation of occluded cells with multiple crevice assemblies (MCAs), as described in the ASTM G78
Standard Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Stainless Alloys in Seawater
and Other Chloride-Containing Aqueous Environments.
In this test, washers make a number of contact sites on either side of the specimens. The number of sites
showing attack in a given time can be related to the resistance of a material to initiation of localized
corrosion, and the average or maximum depth of attack can be related to the rate of propagation. The
large number of sites in duplicate or triplicate specimens is amenable to probabilistic evaluation.
The susceptibility to localized corrosion becomes quite visible once a specimen equipped with these
Teflon washers has been exposed to a corrosive environment for an extended period of time.

... after 30 days in 0.5 FeCl3 + 0.05

10 M NaC

PITTING CORROSION

11

3.3 Pitting
Corrosion

Pitting corrosion is a localized form of corrosive attack that produces holes

or small pits in a metal.
the bulk of the surface remains unattacked.
Pitting is often found in situations where resistance against general
corrosion is conferred by passive surface films.
Localized pitting attack is found where these passive films have broken
down.
Pitting attack induced by microbial activity, such as sulfate reducing
bacteria (SRB) also deserves special mention.

Pitting can be one of the most dangerous forms of corrosion because it is

difficult to anticipate and prevent, relatively difficult to detect, occurs very
rapidly, and penetrates a metal without causing it to lose a significant
amount
Special
case of
of weight.
crevice corrosion:
1. Initiated by inclusions, scratches, or handling damage
instead of deep cracks
2. The presence of static flow conditions and reduced
oxygen availability are less important than in crevice
corrosion

12

Pitting corrosion can produce pits with their mouth open (uncovered) or covered with a
semi-permeable
membrane of corrosion products. Pits can be either hemispherical or cup-shaped.
Pitting is initiated by:
by
1. Localized chemical or mechanical damage to the protective oxide film; water chemistry
factors which can cause breakdown of a passive film are acidity, low dissolved oxygen
concentrations (which tend to render a protective oxide film less stable) and high
concentrations of chloride (as in seawater)
2. Localized damage to, or poor application of, a protective coating.
3. The presence of non-uniformities in the metal structure of the component, e.g.
nonmetallic inclusions.

A local cell that leads to the initiation of a pit

can be caused by an abnormal anodic site
surrounded by normal surface which acts as
a cathode,
cathode, or by the presence of an abnormal
cathodic site surrounded by a normal surface
in which a pit will have disappeared due to
corrosion.

Fig. Local Cathode on a corroded piece of material

13

Alloying can have a significant impact on the pitting resistance of stainless steels.
Conventional steel has a greater resistance to pitting than stainless steels, but is still
susceptible, especially when unprotected.
Aluminum in an environment containing chlorides and aluminum brass (Cu-20Zn-2Al) in
contaminated or polluted water are usually susceptible to pitting.
Titanium is strongly resistant to pitting corrosion.
Proper material selection is very effective in preventing the occurrence of pitting corrosion.
Another option for protecting against pitting is to mitigate aggressive environments and
environmental components (e.g. chloride ions, low pH, etc.).
Inhibitors may sometimes stop pitting corrosion completely.
Further efforts during design of the system can aid in preventing pitting corrosion, for
example, by eliminating stagnant solutions or by the inclusion of cathodic protection.

FIG The pitting of a 304 stainless

steel plate by an acid-chloride solution.

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Sewer Explosion due to Pitting Corrosion

Fig. Corrosion Pits are the primary

source of leaks in water handling
systems

Pitting:
corrosion of a metal surface, confined
to a point or small area, that takes
the form of cavities.
Pitting factor:
ratio of the depth of the deepest pit
resulting from corrosion divided by
the average penetration as calculated
from weight loss.
Pitting resistance equivalent
number (PREN):
an empirical relationship to predict
the pitting resistance of austenitic
and duplex stainless steels. It is
expressed as PREN = Cr + 3.3 (Mo +
0.5 W) + 16N

An example of corrosion damages with shared

responsibilities was the sewer explosion that killed 215
people in Guadalajara, Mexico, in April 1992. Besides the
fatalities, the series of blasts damaged 1,600 buildings and
injured 1,500
people.
*Sewer:
an artificial
conduit, usually underground, for carrying off
waste water and refuse, as in a town or city.

This example of a
pitted surface was
produced by
exposing a specimen
of aluminum
A92519 to 3.5%
NaCl during seven
days. The width of
15
the picture is
approximately 1

Corrosion Pit Shapes

SIDEWAY PITS

THROUGH PITS

Subsurface

Narrow, deep

Shallow, wide

Undercutting

Elliptical
Horizontal grain attack
Vertical Grain Attack

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INTERGRANULAR
CORROSION

17

3.4 Intergranular
Corrosion
Intergranular corrosion refers to preferential (localized) corrosion along

grain boundaries.
or immediately adjacent to grain boundaries, while the bulk of the grains

remain largely unaffected.

This form of corrosion is usually associated with chemical segregation effects

(impurities have a tendency to be enriched at grain boundaries) or specific

phases precipitated on the grain boundaries.
This selective dissolution may lead to the dislodgement of grains.
Intergranular corrosion in sensitized stainless steels and exfoliation in

aluminum alloys represent industrially significant examples of this form of

damage.

Also known as knife- line

attack
18
classic example is the
sensitization of stainless steels

Fig. Severe problem in the welding of stainless

steels, when it is termed weld decay.
FIG. Intergranular corrosion of a failed
aircraft component made of 7075-T6
aluminum (picture width = 500 mm)

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Table 1 Pitting corrosion incidents of aircraft and helicopters

Aircraft

Location
of Failure

Cause

Bell
Helicopter

Fuselage,
longeron

Fatigue, corrosion
and pitting present

DC-6

Engine, master
connecting rod

Piper PA-23

Incident
Severity

Place

Yea
r

From

Serious

AR, USA

1997

NTSB

Corrosion pitting

Fatal

AK, USA

1996

NTSB

Engine,
cylinder

Corrosion pitting

Fatal

AL, USA

1996

NTSB

Boeing 75

Rudder Control

Corrosion pitting

Substantial
damage to plane

WI, USA

1996

NTSB

Embraer 120

Propeller
Blade

Corrosion pitting

Fatal and
serious, loss of
plane

GA, USA

1995

NTSB

Gulfstream
GA-681

Hydraulic Line

Corrosion pitting

Loss of plane, no
injuries

AZ, USA

1994

NTSB

L-1011

Engine,
compressor
assembly disk

Corrosion pitting

Loss of plane, no
injuries

AK, USA

1994

NTSB

Embraer 120

Propeller
Blade

Corrosion pitting

Damage to plane,
no injuries

Canada

1994

NTSB

Embraer 120

Propeller
Blade

Corrosion pitting

Damage to plane,
no injuries

Brazil

1994

NTSB

F/A-18

Trailing-edge
Flap (TEF)
Outboard
Hinge Lug

Corrosion pitting,
fatigue

Loss of TEF

Australi
a

1993

AMRL

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