METL 1313

Introduction to Corrosion
Lecture3

Basic Corrosion
Theory

1
What Is Corrosion?

 One general definition of corrosion is the

degradation of a material through environ-
mental interaction.
 This definition encompasses all materials,
both naturally occurring and man-made and
includes plastics, ceramics, and metals.

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Corrosion

 In this course our focus will be on the

corrosion of metals, with emphasis on
corrosion of carbon and low-alloy steels used
in many structures both above and below
ground.

3
Corrosion

 A significant amount of energy is put into a

metal when it is extracted from its ores,
placing it in a high-energy state.
 Those ores are typically oxides of the metal
such as hematite (Fe2O3) for steel or bauxite
(Al(OH3) for aluminum.

4
Corrosion

 One principle of thermodynamics is that a

material always seeks the lowest energy state.
 Most metals are thermodynamically unstable
and will tend to seek a lower energy state,
which is an oxide or some other compound.

5
Corrosion

 The process by which metals convert to the

lower-energy oxides is called corrosion.
 Corrosion of most common engineering
materials at near-ambient temperatures
occurs in aqueous (water-containing)
environments and is electrochemical in nature.

6
Corrosion

 An aqueous environment is also referred to as

an electrolyte.
 In the case of under-ground corrosion, moist
soil is the electrolyte.
 The corrosion process involves the removal of
electrons (oxidation) from the metal, and the
consumption of those electrons by some other
reduction reaction, such as oxygen or water
reduction.
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Corrosion

 The oxidation reaction is commonly called the

anodic reaction.
 The reduction reaction is called the cathodic
reaction.
 Both electrochemical reactions are necessary in
order for corrosion to occur.
 The oxidation reaction causes the actual metal loss
but the reduction reaction must be present to
consume the electrons liberated by the oxidation
reaction.
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Corrosion

 Oxidation and reduction reactions are

sometimes referred to as half-cell reactions
and can occur locally (at the same site on the
metal) or can be physically separated.
 When electrochemical reactions are physically
separated, the process is referred to as a
differential corrosion cell.

9
Corrosion

 A site where metal is being oxidized is referred

to as the anode or anodic site.
 Electric current in the form of positively
charged ions (defined as a positive flow of
charge) flows from the metal surface into the
electrolyte.

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Corrosion

 Positive current flows in the electrolyte to the

site where oxygen, water, or some other
species is being reduced.
 Those sites are referred to as the cathode or
cathodic sites.

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Corrosion

 There are four necessary components of a

differential corrosion cell.
 An anode must be present
 There must be a cathode
 There has to be a metallic path electrically
connecting the anode and cathode. (normally, that
is the metal itself.)
 The anode and cathode must be immersed in the
same electrically conductive electrolyte (normally,
moist soil or water).
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Corrosion

 Underground corrosion of pipelines and other

structures is often the result of differential
corrosion cells of which a variety of different
types exist.
 Differential corrosion cells include
(differential aeration cells) which can develop
where different areas on a metal surface is
exposed to different oxygen concentrations in
the electrolyte.
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Corrosion

 Differential corrosion cells can be created by

differences in the nature of the pipe surface or
the soil chemistry.
 Galvanic corrosion is a form of differential
cell corrosion in which two different metals
are electrically coupled and exposed in an
electrolyte.

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How Do We Detect Corrosion?

 The electrochemical nature of the corrosion

process provides opportunities to detect and
mitigate corrosion of underground structures.
 We can monitor the voltages and the currents
associated with the corrosion process.
 When a piece of metal is placed in an electrolyte,
such as soil, or water, a voltage or corrosion
potential will develop across the metal/electrolyte
interface because of the electrochemical nature of
the corrosion process.
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Corrosion

 We cannot directly measure metal/electrolyte

interface voltage or corrosion potential, but
by using a voltmeter and a reference cell, we
can measure the voltage or corrosion
potential of metals in an electrolyte.
 Reference cells or electrodes are commonly
referred to as half-cell electrodes.

16
Corrosion

 The measured voltage is referred to as, a

corrosion potential, solution potential, open
circuit potential, or native potential of a metal
in the particular environment in which the
measurement is being made.
 For soil environments, the most common
reference cell/electrode used is the
copper/copper sulfate reference electrode (CSE
or Cu/CuSO4).
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Corrosion

 Potential measurements can be used to

estimate the tendency of a metal to corrode, or
relative resistance of different metals to
corrosion in a given environment.
 Noble metals, such as gold and platinum, have
more positive potentials and are more
resistant to corrode than are the more
common engineering metals such as steel and
aluminum.
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Corrosion

 A galvanic series is a list of metals and alloys

arranged according to their relative corrosion
potentials in a given environment.
 Table 1.1 shows a galvanic series for metals
and other materials in neutral soils and water.
 Table 1.1 shows that carbon has the most
positive potential of the materials listed and
magnesium has the most negative potential.

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Practical Galvanic Series

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Corrosion

 Potentials measured for different metals in a

galvanic series vary somewhat, depending on
the nature of the environment.
 The relative position of the metals is similar
for natural environments such as soil and
seawater.

21
Corrosion

 Another use for corrosion potential

measurements is to establish whether galvanic
corrosion is likely to occur.
 When two metals are electrically coupled in
an environment, the more negative (active)
member of the couple will become the anode
in the differential corrosion cell.

22
Corrosion

 The more positive (noble) member of the

couple will become the cathode in the cell.
 In general, the severity of corrosion due to
galvanic couples tend to increase as the
difference in potential between the two
members of the galvanic couple increases.

23
Corrosion

 Thegalvanic series in table 1.1 indicates that,

when copper is electrically coupled to
commercially pure aluminum in neutral soil or
water, the copper will become the cathode,
accelerating corrosion of the commercially
pure aluminum.

24
Practical Galvanic Series

25
Corrosion

 Table 1.1 also shows that the potential of mild

steel can differ depending on whether the
surface is clean or covered with mill scale.

26
Practical Galvanic Series

27
Corrosion

 The potential of metals is a function of

electrolyte properties, including pH, ion
concentration, oxygen, and moisture content.
 The potential differences that develop on
underground pipelines and other structures as
a result of electrolyte factors can result in
severe corrosion.

28
Corrosion

 Potential measurements are commonly used on

underground pipelines to detect the presence of
different types of differential corrosion cells.
 An electrical connection is made to the pipe, and
the potential of the pipe is measured with respect
to a reference electrode placed over a pipeline.
 The afore mentioned process is shown
schematically in Figure 1.2.

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Pipe/Soil Measurement

30
Corrosion

 Normally, the reference electrode is connected

to the negative lead of a digital voltmeter to
obtain a negative reading.

31
Pipe/Soil Measurement

32
Corrosion

 With this type of measurement, the most

negative regions of the structure are the
anodes and are undergoing accelerated
corrosion due to the differential corrosion
cells.

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Practical Galvanic Series

34
Corrosion Measurements

 Current measurements can be used to detect

differential corrosion cells if the anodes and
cathodes are large.
 Large corrosion cells create long-line currents that
can be detected by measurements made over
pipelines or other underground structures.
 Through Ohm’s law (V = IR), where V is voltage, I
is current, and R is resistance) we know that
current flow through an electrolyte will create a
voltage gradient.
35
How Do We Mitigate Corrosion?

 The principal methods for mitigating

corrosion on underground or submerged
structures are coatings and cathodic
protection (CP).
 Coatings are normally intended to form a
continuous film of electrically insulating
material over a metallic surface to be
protected.

36
Coatings

 The function of a coating is to isolate the

metal from contact with the surrounding
environment (preventing direct contact the
metal).
 Coatings interpose such a high electrical
resistance that electrochemical reactions
cannot readily occur.

37
Coatings

 In reality, all coatings, regardless of overall

quality, contain voids or holes.
 Holes in coatings are referred to as holidays.
 Holidays are formed during application,
transportation, or installation of mill-coated
pipe.
 Holidays in coatings also develop in service as
a result of degradation of the coating, soil
stresses, or movement of the pipe in the ground.
38
Coatings

 Degradation of coatings in service can also

lead to coating disbondment from the pipe
surface, further exposing metal to the
underground environment.
 A high corrosion rate at a holiday or within a
disbonded region can result in a leak or
rupture, even where the coating effectively
protects a high percentage of the pipe surface.

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End

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