Lecture Corrosion

CORROSION
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Durability
Durability is a key material attribute, but is one
of the more difficult attributes to characterize,
quantify, and use for selection
• It is a function not just of the material but of

the environment in which it operates
• There are many mechanisms, some general,
some peculiar to particular materials and
environments
• Material combinations and configurations play a role
Factors Affecting Durability
Figure 17.1
Oxidation
The most stable form of
most elements is an
oxide
Figure 17.2
If the oxide adheres to the material,

it gains weight in either a linear
or parabolic way – if the oxide is
volatile, the sample loses weight
in a linear way Figure 17.3
Oxidation Kinetics
kp – parabolic kinetic constant

Do – diffusion coefficient
Qd – activation energy
Co – concentration gradient
T – temperature
R – gas constant
Mechanisms of Oxidation
When most metals are exposed to air, an ultra-thin
surface film of oxide forms
The oxide film separates the metal from the oxygen – to react
farther either oxygen atoms must diffuse inward through the
film to reach the metal or metal atoms must diffuse outward
through the film to reach the oxygen
The oxidation reaction M + O = MO occurs in two steps:
1)The metal forms an ion and releases electrons M = M2+ + 2e
2)Electrons are absorbed by oxygen to give an oxygen ion O + 2e = O2-
Figure 17.4
The first of these reactions occurs at the metal side of the oxide film while
the oxygen reaction is on the other side – either the metal ions and the
electrons must diffuse out to meet the oxygen, or the oxygen and electron
holes must diffuse in to find the metal
Reduction Potential
Each metal has its own

characteristic potential
called the standard
reduction potential – the
value is relative to a
standard, the hydrogen
standard potential
Figure 17.8
Ions in Solution and pH
Corrosion by acids and alkalis is an electro-chemical reaction
A chemical compound that dissociates

in water increases either the hydrogen
ion concentration or hydroxyl ion
concentration
The pH level of an environment can

initiate corrosion by stimulating
a reaction in which a metal dissociates
into a metal ion and releases electrons
Figure 17.6
Fresh and Impure Water
A metal placed in a conducting solution like salt water dissociated into
ions and releases electrons – the anodic reaction governing this
behavior is:
The electrons accumulate on the

iron giving it a negative charge
that grows until the electrostatic
attraction pulls the metal ions
back onto the surface
Figure 17.7
If two metals are connected together in a cell, a
potential difference appears between them
If a current is allowed, electrons

flow from the anode to the cathode –
causing corrosion of the anode
The reduction potential of each

metal dictates which which is
the anode and which is the cathode –
the metal with the lower potential
acts as the anode
In Figure 17.10, the iron corrodes while

Iron ions to be created at the anode copper is protected , its ions
and hydroxyl ions at the cathode – attract electrons
they react to eventually form rust following the cathodic reaction:
It is not necessary to have two metals for a corrosion
cell to develop – anodic and cathodic reactions
can take place on the same surface
An oxygen concentration
gradient exists between
metal at the surface of the
water and the metal
further immersed in the
water – the potential
difference between the
hydrolysis reaction and the
anodic reaction of iron
Figure 17.11
ions dissociating drives
the corrosion
Selective Corrosion
Wet corrosion often occurs selectively instead of uniformly
• Intergranular corrosion
• Pitting corrosion
• Galvanic attack
• Stress corrosion cracking
• Corrosion fatigue
• Crevice corrosion
Intergranular corrosion
Intergranular corrosion – occurs because grain boundaries
have chemical properties that differ from those of the grain
Martensitic stainless steel (420B)

microstructure show carbides precipitate at
grain boundaries. Chromium, present in the
matrix to guarantee corrosion resistance, is
taken away to form chromium carbides.
This causes a strong reduction in the
corrosion resistance just near the
carbides. This form of corrosion is called
intergranular corrosion and the aspect is
Intergranular
represented in the picture. Corrosion
corrosion of a
develops mainly along the grains
martensitic stainless
boundaries, that is the chromium
steel
impoverished area, susceptible to the
corrosion attack. The component in figure
has failed also because the presence of
tensile stresses.
Intergranular corrosion
Occurs because grain boundaries have chemical properties
that differ from those of the grain
Pitting Corrosion
Pitting corrosion - preferential attack that occurs at breaks in
the natural oxide on metals or at precipitated alloys in
certain compounds
Corrosion fatigue
Corrosion Fatigue – accelerated rate at which fatigue cracks
grow in a corrosive environment
Many materials exhibit a substantial reduction in fatigue life when

exposed to a corrosive environment.
High strength steels are susceptible to substantial reduction in
fatigue resistance in many environments. The endurance limit is
often reduced by a factor of ten from that measured in air.
Galvanic attack
Galvanic attack – appears in alloys with a two-phase
microstructure in which the two regions lie at different
points on the reduction potential scale
Tubesheet corrosion is generally

caused by dissimilarities between
higher alloy, more noble tube material,
and the tubesheet metal.
Stress Corrosion Cracking (SCC)
Stress corrosion cracking is
accelerated corrosion, localized at cracks
in loaded components.
A cracking process that requires the
simultaneous action of a corrodent and
sustained tensile stress.
Stresses may occur due to improper
quenching, welding and other reasons.
Cracks caused by stress corrosion grow
rapidly as the corrosive attack
concentrates at the end of the crack rather
than along its side, because this is the
point of maximum stress.
The micrograph on the right (X500) illustrates

intergranular SCC of an Inconel heat exchanger tube
with the crack following the grain boundaries. (
photo courtesy of Metallurgical Technologies
Crevice Corrosion
This form of attack is generally associated with
the presence of small volumes of stagnant
solution in occluded interstices, beneath
deposits and seals, or in crevices, e.g. at nuts
and rivet heads. Deposits of sand, dust, scale
and corrosion products can all create zones
where the liquid can only be renewed with
great difficulty. This is also the case for flexible,
porous or fibrous seals (wood, plastic, rubber,
cements, asbestos, cloth, etc.).
Crevice corrosion (beneath a seal) on a stainless steel flange exposed to a chloride-rich medium.

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CORROSION

• It is a function not just of the material but of

If the oxide adheres to the material,

kp – parabolic kinetic constant

Each metal has its own

A chemical compound that dissociates

The pH level of an environment can

The electrons accumulate on the

If a current is allowed, electrons

The reduction potential of each

In Figure 17.10, the iron corrodes while

Martensitic stainless steel (420B)

Many materials exhibit a substantial reduction in fatigue life when

Tubesheet corrosion is generally

The micrograph on the right (X500) illustrates

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