By

Iqra Saleem
Department of Chemical & Polymer Engineering
University of Engineering & Technology Lahore (FSD
Campus)

 Corrosion
Corrosion

of Metals
Corrosion of Non-Metals
Mechanism of Corrosion
Factors Influencing Corrosion
Types of Corrosion
Prevention of Corrosion

Corrosion may be defined as the

destruction of metal or an alloy because of
chemical or electrochemical reaction with
its surrounding environment or medium.
3

 Corrosion

is the
disintegration
of
an
engineered
material into its
constituent atoms
due to chemical
reactions with its
surroundings.
4

Corrosion is the primary means by

which metals deteriorate. Most metals
corrode on contact with water (and
moisture in the air), acids, bases, salts,
aggressive metal polishes, and other
solid and liquid chemicals.
Metals will also corrode when exposed
to gaseous materials like acid vapors,
formaldehyde gas, ammonia gas, and
sulfur containing gases.

Electrochemical oxidation of metals in

reaction with an oxidant such as oxygen.

Formation of an oxide of iron due to

oxidation of the iron atoms in solid
solution is a well-known example of
electrochemical corrosion, commonly
known as rusting. This type of damage
typically produces oxide(s) and/or salt(s)
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of the original metal.

Mostly corrosion in metals occurs by

electrochemical attack, since metals have
free electrons which are able to set up
electrochemical cells with in the metals
themselves.
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Reverse Extractive Metallurgy

Most metals exist in nature in combined state.
Example: As Oxides, Sulphides, Carbonates or
Silicates.
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Non-metals such as ceramics and polymers

dont suffer electrochemical attack but destroy
by direct chemical attack.
Example: Ceramic Refractory chemically
attacked at high temperatures by molten salts.
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Corrosion requires a flow of electricity between

certain areas of a metal surface through an
electrolyte. For this, to complete electric circuit
there must be two electrodes and they must be
connected. For electricity to flow there must be
potential difference between electrodes.
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On the surface of the metals there are

numerous tiny anode and cathode areas
because of surface imperfections,
localized stresses, orientation of grains
or variations in the environment.
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2H+ + 2e-
H2

Fe Fe+2 +
2e12

1. Temperature
2. pH
3. Erosion
4. Mechanical Stress
5. Impurities
6. Concentration of Reactant
7. Difference in Electrical Potential
8. Heat Treatment
9. Surface Condition
10. Dissolved Oxygen
13

Temperature
Rate of corrosion is accelerated with
increase in temperature and vice versa.
Temperature Corrosion
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Effect of pH
The main corrosion reaction is spontaneous
under basic conditions, but is accelerated
under acidic conditions. pH Corrosion
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Effect of Erosion
Erosion may remove protective surface
and corrosion takes place at new surface.
Erosion Corrosion
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Effect of Impurities
Greater
impurities
causes
greater
imperfection and greater anode & cathode
thus greater corrosion.
Impurities Corrosion
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Effect of Stress
Stress
corrosion
cracking
caused
by
combined effect of tensile stress and
corrosion environment.
Stress Corrosion
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Difference in Electrical Potential Corrosion

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Effect of Heat Treatment

Improper heat treatments may cause an
increase in the corrosion rate.
Improper Heat Treatment Corrosion
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Effect of Surface
Roughness increases the rate of corrosion.
Greater the roughness greater would be
corrosion.
Roughness Corrosion
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Effect of Concentrated Reactant

Greater the concentration of reactant greater

would be the rate of reaction e.g. acidic
environment (greater H+ thus greater reaction).
Conc. of Reactant Corrosion
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Without Oxygen:
2H+ + 2e- H2
With Oxygen:
O2 + 4H+ + 4e- 2H2O

Effect of Dissolved
Oxygen
Dissolve oxygen in the electrolyte i.e.
solution in which metal is dipped.
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General Corrosion or Uniform Attack

Pitting

1.
2.

Impingement Attack or Erosion-Corrosion

ii. Fretting Corrosion
iii. Cavitation Erosion
i.

Selective Corrosion
Intergranular Corrosion
Galvanic corrosion
Cracking

3.
4.
5.
6.
i.

Corrosion Fatigue

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Uniform corrosion is the

attack of a metal at
essentially the same at all
exposed areas of its
surface.

At no point is the
penetration of the metal
by corrosion twice as
great as the average rate.

In natural environment,
Oxygen is the primary
cause of uniform corrosion
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 The

anodic reaction in the corrosion

process is always the oxidation reaction.

In

acidic environments, the cathodic

process is mainly the reduction of
hydrogen ions

In alkaline/neutral environment, the

reduction of dissolved oxygen is the
predominant cathodic process that
causes uniform corrosion.
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Pitting
corrosion,
or
pitting, is a form of
extremely
localized
corrosion that leads to
the creation of small
holes in the metal.

The driving power for

pitting corrosion is the
depassivation of a small
area,
which
becomes
anodic while an unknown
but potentially vast area
becomes
cathodic,
leading to very localized
galvanic corrosion.

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28

 Once

a pit is formed from localized

corrosion, the pit continues to act as
the anode (losing electrons and mass) .

While

the cathodic reaction remains

O2 + 2H2O + 4e- 4OH-

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 The

presence of an oxydizing cation

(Fe+3, Cu+2, Hg+2, etc.) enables the
formation of pits even in the absence
of oxygen.

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Erosion
corrosion is
a
degradation of material surface
due to mechanical action,
often by impinging liquid,
abrasion by a slurry, particles
suspended in fast flowing liquid
or gas, bubbles or droplets,
cavitation, etc.

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When subjected to high - velocity liquids, undergo a

pitting type of corrosion called impingement attack , or
erosion corrosion .
Copper and brass condenser tubes, for example, are
subject to this type of attack.

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33

Corrosionis a chemical process. It is the

wearing away of a material by another
chemical. This could be an acid as inacid
rainor just oxygen as in rust.
Erosion is the wearing away of rocks by
physical or chemical means. The physical
forces include running water, wind, sand
storms, waves, etc. The possible
chemical here could be the acid rain,
ocean salt effects, oxidation of materials.

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 Fretting-corrosion

is a combined
damage
mechanism
involving
corrosion at points where two moving
metal surfaces make rubbing contact.

It occurs essentially when the

interface is subjected to vibrations
(repeated relative movement of the
two contacting surfaces) and to
compressive loads.
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Fretting corrosion , which results from slight

relative motion (as in vibration) of two
substances in contact, one or both being
metals, usually leads to a series of pits at
the metal interface.
The most common type of fretting is caused
by vibration. The protective film on the
metal surfaces is removed by the rubbing
action and exposes fresh, active metal to
the corrosive action of the atmosphere.
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Pits or grooves and oxide

debris characterize this
damage, typically found in
machinery,
bolted
assemblies and ball or
roller bearings. Contact
surfaces
exposed
to
vibration
during
transportation are exposed
to the risk of fretting
corrosion.
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Cavitation occurs when a fluid's operational

pressure drops below it's vapor pressure
causing gas pockets and bubbles to form and
collapse.
Cavitation-corrosion is particular form of
erosion caused by the "implosion" of gas
bubbles on a metal surface.
It is often associated with sudden variations in
pressure
related
to
the
hydrodynamic
parameters of the fluid (e.g. hydraulic turbine
blades, propellors, stirrer blades, etc.).
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An increase in fluid pressure is often

sufficient to maintain a single phase
fluid, thus avoiding the formation of
vapour bubbles.
This form of corrosion will eat out the
volutes and impellers of centrifugal
pumps with ultrapure water as the fluid.
It will contribute to other forms of
erosion corrosion, such as found in
elbows and tees.

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The locations where this is most likely to occur,

such as:
1. At the suction of a pump, especially if
operating near the net positive suction head
required (NPSHR)
2. At the discharge of a valve or regulator,
especially when operating in a near-closed
position
3. At other geometry-affected flow areas such as
pipe elbows and expansions
4. Also, by processes incurring sudden expansion,
which can lead to dramatic pressure drops

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41

Crevice corrosion refers

to corrosion occurring in
confined
spaces
to
which the access of the
working fluid from the
environment is limited.

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Anodic

reactions

inside

the

crevice:

Fe = Fe2+ + 2e- (dissolution of iron)

The electrons given up by the anode flow to the
cathode (passivated surface) where they are
discharged
in
the
cathodic
reaction:
1/2O2 + H2O + 2e- = 2(OH-)
As a result of these reactions the electrolyte
enclosed in the crevice gains positive electrical
charge in contrast to the electrolyte surrounding the
crevice, which becomes negatively charged.

The positively charged electrolyte in the crevice

attracts negative ions of chlorine Cl- increasing
acidity of the electrolyte according to the reaction:
FeCl2 + 2H2O = Fe(OH)2 + 2HCl

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Galvanic corrosion is
an
electrochemical
process in which one
metal
corrodes
preferentially
to
another when both
metals are in electrical
contact and immersed
in an electrolyte.

Another
term
employed is galvanic
coupling.
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 When

two dissimilar metals are connected

electrically through an electrolyte or salt
bridge one metal will become anodic with
reference to the other and the potential
difference will create a corrosion current
causing the more anodic metal to corrode.

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 For

galvanic corrosion to occur,

three conditions must be present:
1.Electrochemically dissimilar metals
must be present.
2.These metals must be in electrical
contact.
3.The metals must be exposed to an
electrolyte.
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This is a localized type of attack at the

grain boundaries of a metal, resulting in
loss of strength and ductility.
Grain boundary material of limited
area, acting as anode, is in contact with
large areas of grain acting as cathode.
The attack is often rapid, penetrating
deeply into the metal and sometimes
causing catastrophic failures.

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Corrosion along
grain boundaries,
often where precipitate
particles form.

If a metal cracks when subjected to repeated

or alternate tensile stresses in a corrosive
environment, it is said to fail by corrosion
fatigue .

In the absence of a corrosive environment, the

metal stressed similarly, but at values below a
critical stress, called the fatigue limit or
endurance limit , will not fail by fatigue
even after a very large, or infinite, number of
cycles. A true endurance limit does not
commonly exist in a corrosive environment:
The metal fails after a prescribed number of
stress cycles no matter how low the stress.
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Corrosion-fatigue is the result of the

combined action of an alternating or cycling
stresses and a corrosive environment.
The fatigue process is thought to cause
rupture of the protective passive film, upon
which corrosion is accelerated.
If the metal is simultaneously exposed to a
corrosive environment, the failure can take
place at even lower loads and after shorter
time.

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The cracks are generally transgranular

in nature, with little tendency for
branching. However, a few small
secondary cracks may appear in the
vicinity of the main crack.

Control of corrosionfatigue can be

accomplished by either lowering the
cyclic stresses or by variouscorrosion
control measures.
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