CORROSION

 INTRODUCTION:
Corrosion is the destruction or deterioration of
material because of reaction with its environment,
or destruction of materials by chemical or
electrochemical reaction with environment rather
than straight mechanical.
The importance of corrosion studies always
concentrated on three main things:

The first area of significance is economic; including the

objective of reducing losses resulting from the
corrosion of material.
The second is improved safety of operating
equipment, because corrosion may fail with
catastrophic consequences. Examples are pressure
vessels, radioactive material, boilers, etc.
The third is conservation of metal resources because
the world’s supply of these resources is limited and
the wastage of them includes losses of water
reserves associated with the production and
fabrication of metal structures.

Environment plays a big role in corrosion of metals.

Practically all environments are corrosive to some
degree; some examples are air and moisture;
fresh,
distilled, salt and mine waters; rural, urban and
industrial atmospheres; steam and other gases
such as chlorine gas, ammonia, H2S, SO2 and fuel

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gases; mineral acids such as HCL, H2SO4 and
HNO3; organic acids such as acetic and formic;
solvents, vegetable and petroleum oils; and food
products .On the other hand, corrosion damage
cause economic loss to the country as well as the
environmental problems, either by direct losses or
indirect losses.

1) By Direct losses: and this represents the costs of

replacing corroded structures, such as
condenser tubes, pipelines, metal roofing etc.,
including necessary labor, also include the
extra cost of using corrosion-resistant metals
and alloys or chemicals, such as corrosion
inhibitors .The first studies indicate that the
cost of corrosion in Jamahiriya industrial and
oil fields up to 50 million Dinars per year.

2) Indirect losses: Corrosion failures can sometimes

cause many unexpected problems that need
money and control to avoid them. Examples
of indirect losses are as follows :

I) Shut down: Unexpected corrosion failures in any

plant need shut down or stopping of the plant to
repair the failure. In this case the total cost will
be replacement of corroded part plus the cost of
the lost production.
ii) Lost of product: losses of oil, gas, or water occur
through a corroded pipe system until repairs are
made. Gas leaking from a corroded pipe may
enter the basement of a building and cause an
explosion.

iii) Contamination of product: In many cases the

market value of the product is directly related to
its purity and quality. A small amount of

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 corrosion, which introduces certain metal ions
into the solution, may cause catalytic
decomposition and contamination of a product.
v) Effects on safety: The handling of hazardous
materials, such as toxic gases, strong acids and
radioactive substances demands the use of
materials of construction which minimize
corrosion failures.
Corrosion failure of a small component may
result in failure of the entire structure. Corroding
equipment can cause some fairly harmless
compounds to become explosion.
vi) Appearance: Badly corroded and rusted
equipment in plant or any used metal surface
would leave a poor impression on the observer.
Much money is spent on painting of cars and
choosing expensive material like stainless steel
or aluminum for use in out side surfaces or trim
of buildings.

Sheet

Auto body
Steel mil (Atmosphere) Rust
Iron Reduction
Mine ore Refining
Casting
Rolling
(Iron Shaping
oxide) Hydrated
Underground iron oxide
Pipeline
Pipe (Soil and water)

Fig. (1)

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 PRINCIPLES OF CORROSION:

The choice of any structural material depends on

many factors, including its corrosion resistance.
As mentioned before the cost and corrosion
resistance of the material is usually the most
important factors. As shown in the following
figure these factors affect the choice of an
engineering material.

Corrosion
ecnatsiseR

ytilibaliavA
tsoC

lairetaM

htgnertS
ecnaraeppA

ytilibacirbaF

Fig. (2)
Corrosion resistance or chemical resistance of
any material depends on many factors.
Its complete and comprehensive study requires
knowledge of several fields of scientific
knowledge as indicated in the figure below:

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 Fig. (3) Electrochemical

Physical
chemical Corrosion
resistance

Metallurgical

Thermodynamic

Thermodynamics and electrochemistry are of

great importance for understanding corrosion.

For example: if we ask a question:

Will corrosion occur for any system?

The answer will be:

Depends on thermodynamics of the system
(studying electrochemical equilibrium, electrode
potential, chemical equilibrium).

The second question will be if the system has a tendency for

corrosion then how fast will be?

The answer will be:

Depends on Kinetics. (Studying the kinetic of the
rate of corrosion reaction is controlled by the system)
rate of electron transfer.
 ELECTROCHMICAL CONCEPT OF CORROSION

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Corrosion of metal in an electrolyte (in contact with
moist soil or water )is basically an electrochemical
reaction. The corrosion reaction usually involves
anodic areas (anodes) at which metal solution
(corrosion) takes place, and cathodic areas
(cathodes) at which a reducing action, not usually
affecting the metal occurs. Electrical current flows
from the anode to the cathode in the electrolyte
and from cathode to anode in the metal. An area
will be anodic or cathodic as determined by its
tendency to go into solution.
The tendency for any chemical reaction to go
including the reaction of a metal with its
environment is measured by free energy change Δ
G (delta). The more negative the value of Δ G, the
greater is the tendency for the reaction to go. So if
we consider the following reaction at 25˚ C.

i) Mg + H2O(1)+1/2O2(g) Mg(OH)2(S)

ΔG˚=-142,600 cal.

ii) Cu+H2O(1)+1/2O2(g) Cu(OH)2(S)

ΔG˚= -28,600 cal.

iii) Au+3/2H2O(1)+3/2O2(g) Au2(OH)3 (S)

ΔG˚=+15,700 cal.

The values of ΔG shows that Mg has high tendency

to corrode in aerated water environment than
copper. Gold in equation (iii) has no tendency at
all.
Correspondingly does not corrode in aqueous
media.

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The tendency for a metal to corrode can also be
expressed in terms of electromotive force (e.m.f)
of the corrosion cells. Since electrical energy is
expressed as volts x Coulombs (joules), the
reactions between ΔG in joules and e.m.f in volts,
E, is ΔG= - n F E

Where n= No. Electrons involved in reaction

F= Faraday (96,500 Coulombs)
Therefore the greater the value of E for any cell,
the greater is the tendency for the overall reaction
for the cell to go.

 Corrosion of Iron: Since we are primarily

concerned with the corrosion of iron as metal used
in many plants exposed to environment (moist,
soil, or water) the electrochemical corrosion
reaction of iron will be as follows:

If piece of iron is in contact with solution containing

(H+). The iron Fe will tend to go to solution and H2
gas will deposit on the surface of iron.
The over all reaction may be written as:

Fe + 2H+ Fe++ + H2
This reaction may be broken down into two
separate reactions as follows:

At the anode Fe Fe++ + 2e

At the cathode 2H+ + 2e H2

Electrons are transferred in the metal from the
anode to the cathode, Electrical current flowing in
the opposite direction from the cathode to anode.

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 Fig. (4)
H+ H+ Fe++

Iron surface Environment

e-

Iron metal
e-

In general in all corrosion processes, the anodic

reaction is the oxidation of metal to its ion giving
electrons e.g.

M M+n + ne.

On the other hand there will be cathodic reaction

to consume the electrons produced by metal as a
reduction reaction.
The most common cathodic reactions are
frequently encountered in metallic corrosion are:

Hydrogen evolution
2H+ + 2e- H2
Oxygen reduction (acidic)
O2 + 4H++4e- 2H2O
Oxygen reduction (basic)
O2 +2 H 2O +4e- 4OH-
Metal ion reduction
Mn+ + ne- M

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Therefore the pre-requirements for corrosion are:

I) Anodic process: dissolution of metal (electron

production)

ii) Cathodic process: electron consumption

iii) Electron-movement in the metal i.e. (conductivity)

iv) Ion-movement in the solution i.e. (electrolytic

conductivity)

 Types or (forms)of corrosion :

1.Uniform Attack: It is the most common form of
corrosion. It is normally characterized by a
chemical or electrochemical reaction, which
proceeds uniformly over the entire exposed
surface, or covers a large area.

Uniform attack can be prevented or reduced by :

a) Proper materials.
b) Inhibitor.
c) Cathodic protection.
d) Protective coating

2. Galvanic corrosion or two-metal corrosion :

When two dissimilar metals with different
potentials are immersed in a corrosive or

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 conductive solution, this potential differences
produce electron flow between them. The
more active metal (less resistant) becomes
“anodic” and less active metal (more
resistant)”cathodic”.

3. Pitting Corrosion :
is localized accelerated attack resulting in
the formation of pits or holes in the metal.

4. Erosion Corrosion :
is the acceleration or increase in rate of
attack on a metal because of relative
movement between a erosive & corrosive
fluid and the metal surface.

5. Stress Corrosion :
Stress Corrosion or stress cracking is the
combined effect of static tensile strength and
the corrosive environment on a metal.
For stress corrosion to occur, both the
presence of tensile stress and specific
corrosive environment are necessary.

6. Microbial Corrosion :
Is the deterioration of a metal by corrosion
processes, which occur directly, or indirectly
as a result of the activity of microorganisms
which are present in a variety of environments
such as soil, natural water, seawater and in
natural petroleum products. A good example is
the sulfur-oxidizing bacteria, which are
capable of oxidizing elemental sulfur, or sulfur
bearing compounds to sulfuric acid, creating

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 extremely corrosive conditions: (aerobic
sulfur-oxidizing bacteria)

2S + 3O2 + 2H2O 2H2SO4

(In the presence of Thiobacillus, Ferrooxidans)

7.Underground or Soil Corrosion:

Corrosion conditions for any metal structure
buried underground vary over a wide range
according to the soil medium.

The factors affecting corrosiveness of a soil are:

a) its acidity
b) degree of aeration
c) its moisture and salts content
d) electrical conductivity
e) presence of bacteria and micro-organisms
f) soil texture (particle size )
Soil corrosion is purely electrochemical in character
CORROSION CONTROL:
Corrosion damage can be completely avoided
only under ideal conditions.
Although such ideal conditions are impossible to
apply, it is possible to minimize corrosion
considerably.
Since the types of corrosion are so numerous the
conditions under which corrosion occurs are so
extremely varied, it is not surprising that
different methods are used to deal with
corrosion problems.
The most common ways for controlling
corrosion are as follows:
1. Protection by proper design:
A proper selection of the material for any
particular corrosive environment and consulting
a corrosion engineer during the design time are

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the best means of controlling and even
preventing corrosion.
For Example:
Avoidance of dissimilar metal contact in the
presence of a corroding solution. Like in water
supplying system galvanized iron tanks are
under rapid corrosion in the presence of copper
pipes, because galvanic cell will form between
Cu and Zn.

2. Improving the characteristics of the metal:

Impurities in metal causes heterogeneity, which
decreases corrosion resistance of metal .An
increase in both strength and corrosion
resistance of most commercial metals is best
improved by alloying them with suitable alloying
elements.
Example of alloying iron base metal, which is
most significant because of the wide range use
of stainless steel.
Many alloying elements (like P, Cu, Si, Al…) are
useful in giving iron a limited corrosion resistant
only. However, alloying effect of Cr. with iron
increases corrosion resistance in almost all
environments.

3. Cathodic Protection:
Is a method of preventing or reducing metal
corrosion in an electrolytic medium by supplying
electrons to the metal structure to be protected.
In all corrosion cells, corrosion occurs only at the
anode, while various reactions may take place at
the cathode, the metal does not go into solution
and is protected from corrosion .If a metal
structure in the soil or immersed in water is
made the cathode so that the surface picks up

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 current from the electrolyte ,the structure will
not corrode. Cathodic protection can be
achieved in either of two ways; by the use of
galvanic (sacrificial) anodes, or by impressed
current.

Galvanic anode systems employ reactive metals as

auxiliary anodes electrically connected to the
structure to be protected. The difference in
potentials between the anode and structure, as
indicated by their relative positions in the
Electro-chemical series, causes a positive
current to flow in the electrolyte from the anode
to metal structure, so that the whole surface of
structure be comes cathode.
Impressed-current systems employ inert or non-
galvanic anodes with an external source of D.C.
power to impress a current from anode to
cathode.

The following figures show the principles of both systems:

The principle of cathodic
Protection by sacrificial Anodes.

Fig. (5)

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 Wires joining sacrificial anodes to pipe line

Current Sacrificial anodes near to pipe

Pipeline buried in earth

The principle of cathodic protection

By impressed current.

Transformer Rectifier

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Ground
Level

Tank Current
Anode

Fig. (6)

4. Use of Inhibitors:
A corrosion inhibitor may be defined as a
substance which when added in small quantities
to the aqueous corrosive environment,
effectively decreases the corrosion rate of a

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 metal. Inhibitors are organic or inorganic
substances that dissolve in the corroding
medium, but are capable of forming a protective
layer of some kind at either the anodic or
cathodic areas.

Anodic inhibitors: (such as chromate,

phosphate, or other ions of transition elements
with a high oxygen content). These compounds
are adsorbed on the metal surface forming a
protective film or barrier thereby reducing the
corrosion rate.

Cathodic inhibitors: (such as amines. hetrocyclic

nitrogen compounds are capable to adsorb at
the metal surface and decrease cathodic
reaction e.g.

2H + 2e- H2 in this case it decrease the

hydrogen diffusion in the medium.

5. Protective coatings:
It is probably the oldest of
the common procedures for corrosion prevention.

A coated surface isolated the underlying metal

from the corroding environment. There are
organic coatings like paints or inorganic-like
metallic coatings.

 CORROSION MONITORING :
The following figure summarizes the techniques available for
monitoring corrosion in an operating plant.

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 Thickness
Measurement

Hydrogen
Visual
probes
Inspection

Weight loss coupon CORROSION Sentinal

And other test pieces MONITIRING Holes

Electrical resistance Linear polarization

Probe measurement

Measurement of plant
Corrosion potential

Fig. (7)

References

1. FONTANA, M.,”Corrosion Engineering”, international

edition 1987, Mc Graw Hill Book Co. (third edition )

2. “Corrosion for Science and Engineering”, second edition

published 1995, produced by Long man Singapore publishers
(Pte) Ltd.

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3. D.L.Piron, “The Electrochemistry of Corrosion”, second
printing 1991, published by NACE International.

4. ASM Hand book, formerly Ninth Edition, Metals Handbook,

volume 13 Corrosion, page 118 / forms of corrosion,
prepared under the direction of the ASM INTERNATIONAL
Handbook Committee.

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