UMIST

Corrosion and Protection Centre

Module 0 Introduction to Corrosion

Module Notes - Localized Corrosion

September 2003
This document is 2002 - 2003, the Corrosion and Protection Centre, UMIST.

All rights reserved

Localized Corrosion
Learning outcomes at the end of the course you should be able to

Identify the main forms of localised corrosion

Provide simple explanations of the mechanisms of localised corrosion processes

Name chloride ions as a main environmental initiator of localised corrosion

The various forms of localized corrosion tend to be a more severe problem than normal
general corrosion, since they lead to more damage to structures for a given loss of metal.
Localized corrosion problems tend to occur most commonly when general corrosion has
been limited by various means, but the protection is incomplete, and fails at local points.
Since the rate of corrosion processes is often controlled by the rate of supply of oxygen to
the metal surface, this may result in the same metal loss as in general corrosion, but only
at the points of local breakdown, with consequent rapid attack.

Sources of Localized Corrosion

Localized corrosion may be caused by variations in the environment seen by different
regions of the metal, by inherent variations in the structure or composition of the metal,
or by the effects of the mechanical loading experienced by the component.
Environmental variations that may be important include oxygen concentration, chloride
ion concentration, pH and flow rate.

Important metallurgical variations generally involve segregation of the alloying elements

in the metal, such as the presence of second phase precipitates, inclusions and grain
boundary segregation.

Mechanical factors that may be important include both static stress, which leads to stress
corrosion cracking, and fluctuating stress, which results in corrosion fatigue.

Types of Localized Corrosion

Galvanic Corrosion
A extreme form of segregation occurs when two
dissimilar metals are coupled together. For example,
if a piece of iron is connected to a piece of copper in
aerated sodium chloride solution, oxygen reduction
will occur on the surface of both the copper and the
iron. However only the iron will be able to corrode.
Consequently if the areas of the two metals are the
same, the iron will corrode twice as fast as it would
in the absence of the connection to the copper.

2002 - 2003, Corrosion and Protection Centre, UMIST Module 0, Localized Corrosion - Page 1
 Table 1 Standard emf series Table 2 Galvanic Series in Seawater

o o
Reaction E at 25 C,
(V vs NHE)
Au-Au3+ +1.498 Platinum
2+
Pt-Pt +1.2 Gold
Pd-Pd2+ +0.987 ? Graphite
+
Ag-Ag +0.799 Noble or Titanium
2+
Hg-Hg2 +0.788 cathodic Silver
Cu-Cu2+ +0.337 Chlorimet 3 (62 Ni, 18 Cr, 18 Mo)
Hastelloy C (62 Ni, 17 Cr, 15 Mo)
H2-H+ 0.000 18-8 Mo stainless steel (passive)
18-8 stainless steel (passive)
2+
Pb-Pb -0.126 Chromium stainless steel 11-30% Cr
2+
Sn-Sn -0.136 (passive)
Ni-Ni2+ -0.250 Inconel (passive) (80 Ni, 13 Cr, 7 Fe)
2+
Co-Co -0.277 Nickel (passive)
2+
Cd-Cd -0.403 Silver solder
Fe-Fe2+ -0.440 Monel (70 Ni, 30 Cu)
3+
Cr-Cr -0.744 Cupronickels (60-90 Cu, 40-10 Ni)
2+
Zn-Zn -0.763 Bronzes (Cu-Sn)
Al-Al3+ -1.662 Copper
2+
Mg-Mg -2.363 Brasses (Cu-Zn)
Na-Na+ -2.714 Chlorimet 2 (66 Ni, 32 Mo, 1 Fe)
K-K+ -2.925 Hastelloy B (60 Ni, 30 Mo, 6 Fe, 1 Mn)
Inconel (active)
Nickel (active)
Lead-tin solders
18-8 Mo stainless steel (active)
Ni-Resist (high Ni cast iron)
Chromium stainless steel, 13% Cr
(active)
Cast iron
Steel or iron
2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
Cadmium
Active or Commercially pure aluminium (1100)
anodic Zinc
? Magnesium and magnesium alloys
After de Bethune and Loud from INCO test results

Similarly in an aluminium alloy containing iron, iron-aluminium inter-metallic particles

will be precipitated in the aluminium. Unlike the normal aluminium surface, which is
protected from corrosion by an insulating layer of aluminium oxide, the iron-aluminium
particles are good sites for hydrogen evolution, and this leads to intense local corrosion
around the precipitates.

The EMF Series (Table 1) and the Galvanic Series (Table 2) are often used to determine
which metal of a couple is liable to corrode. The EMF Series has the advantage of being
based on a precisely quantifiable parameter, but unfortunately passive metals may
operate as stable cathodes at potentials well above the equilibrium potential,
consequently it gives a rather poor indication of the behaviour to be expected. The
Galvanic Series has been derived from exposure of samples in the specified environment,
and therefore gives a better indication of practical performance. However, even the
Galvanic Series should be used with some caution, as the severity of any galvanic
corrosion since this depends on such factors as the electrical resistance of any passive
films, the conductivity of the electrolyte and the kinetics of the cathodic reaction on the
cathodic half of the couple.

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Differential Aeration
Differential aeration occurs when two areas
of a piece of metal are exposed to regions of
solution of different oxygen content. In this
case the cathodic reaction of oxygen
reduction only occurs at the site at which
oxygen is readily available, while the metal
dissolution occurs over the entire surface of
the sample. At the site of the oxygen
reduction excess hydroxyl ions are produced,
causing the pH to rise. For many metals, such
as iron and copper, this results in the
deposition of a passive film of metal oxide or
hydroxide, with the result that the rate of
metal dissolution at this site is retarded.
Correspondingly the metal dissolution
reaction is accelerated in the oxygen-free
region of the solution.

Crevice Corrosion and Deposit Attack

For metals that are normally protected by a
passive oxide film, such as stainless steel, the
formation of forms of differential aeration cell
by the presence of crevices in the structure can
lead to very severe corrosion. Considering, for
example, the use of stainless steel in seawater,
when the structure is first immersed in
seawater, the solution both inside and outside
the crevice will be oxygenated, and the
corrosion rate of the steel will be low due to
the protective action of the passive oxide film.
However, the oxygen inside the crevice will
eventually be used up by the slow corrosion
occurring, while the steel outside the crevice
will continue to be in contact with aerated
solution. The steel inside the crevice will
continue to corrode, leading to the production
of positively-charged metal ions inside the
crevice. These react with hydroxyl ions to
precipitate iron hydroxide. Because of the
removal of hydroxyl ions from solution by this
process, the pH in the crevice goes down.
Thus the solution in the crevice becomes more
and more acid, until eventually the passive
oxide film can no longer be maintained, and the steel starts to dissolve actively. This
further reinforces the acidification of the crevice, and severe corrosion occurs inside the
crevice. Similar problems may also occur under deposits of dirt, sand etc., and in this
case the resulting corrosion is called deposit attack.

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It should be emphasized that crevice corrosion requires a passive external surface in
order to proceed. For metals that are actively corroding, such as carbon steels in
seawater, the conditions in a crevice do not become acidic, because the accumulation of
metal ions stifles further corrosion, and in this case the crevice is protected from
corrosion. Problems are experienced in crevices in carbon steel structures exposed in the
atmosphere, but these are due to the retention of moisture in the crevice, not conventional
crevice corrosion.

Pitting
Under suitable circumstances a corrosion
mechanism similar to crevice corrosion can
occur on plain metal surfaces. For various
reasons the passive film breaks down locally,
the region of solution in contact with the
metal becomes acidic and starts to corrode
rapidly. The resultant hole is known as a pit,
and the process as pitting corrosion. Pitting corrosion of an aluminium tube.

Dealloying

Dezincification of brass note the porous copper plug and

the continuous layer of copper (from corrosion.ksc.nasa.gov)
Alloys are inherently made of dissimilar metals, which may have very different corrosion
properties. For example cast iron consists of iron, which is relatively easily corroded, and
carbon, which is essentially inert. In normal carbon steels the carbon is dispersed in the
steel as fine precipitates of iron carbide, which leaves a deposit of very finely divided
carbon when it dissolves. However in grey cast iron the carbon is present as flakes of
graphite. When this corrodes, the graphite is left behind, and retains the shape of the
original casting. This process is known as graphitic corrosion or graphitisation (some
workers argue that the latter term relates to another form of degradation and should not
be used here, but it is widely used), and may be quite dangerous, since the component
appears to be intact, although the graphite has little strength.
A similar process can occur with alloys such brass, from which the zinc can dissolve,
leaving a spongy mass of copper behind. Again this does not change the shape of the
object, but the strength is markedly reduced.

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Intergranular Corrosion
Grain boundaries in metals and alloys tend to be
sites of significant changes in composition. Because
of the irregular structure of the grain boundary it is
easier to fit impurity atoms in, and also diffusion of
atoms is faster. Consequently grain boundaries tend
to have different properties from the bulk of grain.
This leads to enhanced corrosion either at the grain
boundary (if it is less corrosion resistant than the
grain), or immediately next to it (if the grain
boundary is more noble).

Exfoliation of an aluminium girder from a

crashed WW 2 aircraft

Stainless steels are corrosion resistant because of the chromium content, which permits
the formation of a thin, highly protective film of chromium oxide on the steel surface. In
order for the steel to be corrosion resistant, the chromium content must be greater than
about 9%. For this reason stainless steels have chromium contents that are typically in the
range 13 to 20 %. Unfortunately however, if the steel also contains carbon, it is possible,
if the steel is heated to a certain temperature range, for the chromium and carbon to
combine to form precipitates of chromium carbide. Because of the faster diffusion in the
grain boundary the precipitates form preferentially here. Furthermore, because of the
much faster diffusion of carbon than chromium, this precipitation tends to consume most
of the chromium in the neighbourhood of the grain boundary, and the effective grain
boundary chromium concentration is insufficient to keep the metal protected. The
resulting corrosion is known as intergranular corrosion, and is a serious problem in
welded structures. It can be controlled either by reducing the carbon content to a very low
level, or by adding elements such as titanium or niobium, which form carbides in
preference to the chromium.
During rolling the grains in a metal tend to be flattened into a pancake shape, and if such
an alloy is subject to intergranular corrosion, the structure can separate into a series of
layers. This is known as exfoliation, and often occurs with aluminium alloys.

Flow Effects
Flow of solution tends to accelerate corrosion
processes by increasing the rate at which oxygen
gets to the surface of the metal (an exception to
this occurs for passive metals, when the improved
oxygen supply can help to maintain passivity).
When flow conditions become turbulent, the
corrosion problems can become much more
severe, and serious localized corrosion is often
observed at joints and bends in pipework carrying
water.
Erosion corrosion of a pump impeller

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More serious problems can occur if the fluid contains entrained air bubbles or particles of
solids, both of which further enhance the transport of oxygen to the metal surface, and
also tend to mechanically damage and remove protective films of corrosion product.
These processes are known as impingement and erosion-corrosion.
If the solution velocity becomes high enough, vapour bubbles may form at low-pressure
regions. The subsequent collapse of these leads to a combination of corrosion and
mechanical damage known as cavitation.

Mechanical Aspects of Corrosion

It is often found that the joint action of corrosion and mechanical stress is more damaging
than either alone. One aspect of this aspect of this interaction is the enhanced failure of
metals by cracking in the presence of stress. In the case of a static stress the resultant
failure is termed stress corrosion cracking, while for alternating stresses the process is
called corrosion fatigue. Additionally, the action of mechanical stress can enhance
corrosion and related processes. Thus mechanically deformed metal tends to corrode
more rapidly, while rubbing surfaces may suffer from accelerated corrosion known as
fretting corrosion.

The Effect of Stress and Strain on Corrosion

Elastic stress does not usually cause much change in corrosion behaviour, but as soon as
plastic deformation occurs, the metal tends to become significantly more active, either
because the oxide film which normally limits the rate of corrosion is disrupted by the
deformation, or because the greater number of dislocations in the strained metal make the
corrosion process easier.

Stress Corrosion Cracking

Stress corrosion cracking of a large stainless steel float

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If the rate of corrosion at sites at which the protective oxide film is ruptured is sufficient
to cause more plastic strain at the tip of a notch or crack, it is possible for this enhanced
corrosion to propagate into the metal, with the corrosion causing the plastic strain, and
the plastic strain causing the corrosion. This process is called stress corrosion cracking.
Because of the need for a fairly delicate balance between the tendency to corrosion and
the generation of plastic strain, this phenomenon is observed only in specific
combinations of metal and environment, although as our knowledge of the subject
increases, so we find more cases of problems. A general requirement is that the metal
should be protected by a good passive film, but one that reforms slowly when damaged.
Common systems giving rise to stress corrosion cracking are:
Brass and ammonia (often in local atmospheres).
Austenitic stainless steels and chloride solutions (70C).
Carbon steels in caustic, carbonate/bicarbonate, nitrate and phosphate solutions.
High strength aluminium alloys in water or water vapour.

Hydrogen Embrittlement
Many metals are made brittle by the presence of dissolved hydrogen. The reasons for this
are not known, but this leads to many problems that are similar in result to stress
corrosion cracking (indeed the latter term is often used to cover both types of failure).
The hydrogen may come from many sources, such as:
Welding.
Electroplating.
Contact with gaseous hydrogen.
Corrosion, especially in the presence of sulphides.

In general higher strength materials are more susceptible to hydrogen embrittlement, the
major problems occurring with high strength steels. As a general rule face centred cubic
materials, such as austenitic stainless steels, are less susceptible to hydrogen
embrittlement, although it seems probable that the stress corrosion cracking of high
strength aluminium alloys in water is a hydrogen embrittlement process.

Liquid Metal Embrittlement

A process similar to stress corrosion cracking can occur if liquid metals come into
contact with a metal. For example mercury will cause brass to crack, and stainless steel
will crack in liquid zinc.

Corrosion Fatigue
The process of metal fatigue is responsible for the majority of mechanical failures. When
combined with a corrosive environment the process is known as corrosion fatigue. The
effects of corrosion on fatigue crack initiation and growth are still not fully understood,
but in general the effect is to increase the rate of both processes. The mechanisms by
which this is thought to happen are similar to those of stress corrosion cracking and
hydrogen embrittlement, but because of the more extreme mechanical damage, the
environments in which the effects are seen are far less specific.

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Fretting Corrosion
If two metal surfaces are rubbed together, the oxide film which is normally present, and
which reduces the rate of corrosion, may be removed, thereby allowing corrosion to
occur more quickly. The oxide debris may also act as an abrasive, particularly if the
amount of movement is small, and the oxide remains in the joint. This process, which can
lead to very rapid wear of mating surfaces, is known as fretting corrosion.

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