Chapter 4

Forms of corrosion

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FORMS OF CORROSSION
Several forms of corrosion can be identified based on the
appearance of the corroded metal.

A. Uniform Corrosion. B. Localized Corrosion.

 Atmospheric Corrosion  Pitting Corrosion.
 Galvanic Corrosion
 Stress Cracking Corrosion.

 Erosion-corrosion
 Crevice Corrosion.

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 A- Uniform Corrosion:

• Uniform corrosion is defined as a corrosion process with a uniform

metal dissolution rate over the entire surface area (or a large fraction
of the surface area) exposed to the corrosive environment.

• In such type of corrosion there is a uniform decrease in the

volume of the metal due to direct contact with the surrounding
environment.

• Examples:
1. Dissolution of (Zn and Al metal in acids) and (Pb metal in base)
2. Rust! steel exposed to environment.
Uniform in nature
leaves scale or deposit over entire exposed area
Rust is a hydrated iron-oxide – Fe(OH)3 or Fe2O3.3H2O. 3
Uniform Corrosion:

Atmospheric Corrosion
Atmospheric corrosion takes place due to the direct contact
between a metal and its surrounding atmosphere
 Types of atmosphere are encountered:

 Gas type: contain mainly oxygen gas(21% by volume) and

water vapor ( 1%).
 Liquid type: contain mainly water and dissolved oxygen.

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Factors affecting atmospheric corrosion:
 Type of metal or alloy
 Type of atmosphere (dust, humidity, pollutant. Water vapor, gases,…)
 Temperature (the corrosion rate increases with increasing temp.).
 Time (the extent of corrosion increases with increased exposure time).
 Surface Condition:
 more roughness, more corrosion

 The presence of foreign matter influence the speed of corrosion

 The formation of a surface oxide layer and its properties

Protective Non Protective

Non active active
Adherent Non adherent
Oxide layers Non porous, dense and Porous
compact
Ex: Al Ex: iron rust
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Uniform Corrosion:

Galvanic Corrosion
Causes:
 Dissimilar metals
 Electrolyte (differential aeration corrosion)

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Mechanism of galvanic corrosion:
For two different metals M1 and M2 when exposed to the same
corrosive environment, if M1 is more active than M2

 Anodic reaction:
M1 M2
The more active metal act as anode
Anodic metal will be corroded.
M1  M1 n+ + ne- (n=1, 2, 3, …)

 Cathodic reactions:

(I) O2 + 4H+ + 4e-  2H2O Eo = 1.23 V O2 rich acidic media

OR
(II) O2 + 2H2O + 4e-  4OH- Eo = 0.401 V O2 rich non acidic media
OR
(III) 2H+ + 2e-  H2 Eo = 0.0 V O2 poor acidic media
OR
(IV) 2H2O + 2e-  H2 + 2OH- Eo = -0.828 V O2 poor non acidic media
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Examples of galvanic corrosion
 Metal plating

Steel Welding

Steel rivet
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 After immersion in Sea water for 6-10 After immersion in Sea water for 6-10
months, the steel rivets are severely months, the steel bar is severely
attacked & Cu-bar remains unchanged. attacked & Cu-rivets remain unchanged.
Large cathode/small anode Small cathode/large anode
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Small anode + large cathode = corrosion catastrophe
Factors affecting galvanic corrosion
Potential Difference (P.D.)
As the P.D increases the galvanic corrosion increase
The rate of corrosion of (Zn/Fe) galvanic cell (P.D.= 0.32V) is slower
than corrosion of (Zn/Cu) galvanic cell (P.D.= 1.1V).

Distance
As distance increase as corrosion rate decrease.

Area
As the Area (C/A) ratio increases the galvanic corrosion increase.
As the Area (C/A) ratio decreases the galvanic corrosion decrease.

Small anode + large cathode = corrosion catastrophe

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Uniform Corrosion:

Galvanic Corrosion
Differential Aeration Cell (oxygenation)cell
This type of corrosion takes place due to the difference in
oxygen concentration on the same metal or alloy.
Differential aeration cells are
concentration cells in which differing
concentrations of oxygen is the driving
force for corrosion. A differential
aeration cell is shown in the Figure.
•In a differential aeration cell, the
electrode in lower O2 pressure acts M | poor O2 electrolyte || electrolyte rich O2 | M
as the anode and the one in higher Anode (-) Cathode (+)
O2 pressure acts as the cathode Corroded Area
O2 rich area

Zn water line

O2 poor area bright Corrosion of water tanks

KCl
corrosion
Rich oxygen

Partially immersed metallic plates. Corroded area

Poor oxygen
‫هيكل السفينة ‪ship hull‬‬
Localized corrosion: Causes: concentration gradients in
electrolyte cause some areas high in ion
Crevice Corrosion concentrations that accelerate oxidation

Crevice corrosion takes place in the following stages:

Initial stage:
MMz+ + ze– anodic
O2 + 2H2O+4e– 4OH– cathodic
These reactions occur uniformly inside and outside the crevice as
shown in the figure

Later stage
Examples of Crevice or Concentration Cell

 Good example – crevices or under deposits of dirt or corrosion

products where the solution is stagnant.
 Crevice must be wide enough to allow solution to penetrate
yet narrow enough for stagnancy (i.e. few thousandths of an
inch).
Crevice corrosion between
Rubber pads just accelerated
pipe and I-beam:
the attack – why???
Localized corrosion:

Pitting Corrosion
 Extremely localized corrosion that leads to the creation of
small holes (pits) in the metal surfaces where, electrolyte is
aggressive and stagnant.
 Pitting results from a local breakdown of the passive layer by
aggressive anions.
• A galvanic cell is produced Electrolyte NaCl

Cl–
where the metal inside the pit O2 + H2O + 4e– 4OH– O2 + H2O + 4e– 4OH–

Passive layer
acts as anode while the passive Passive layer

film acts as cathode as shown.

FeCl2 + H2O 2e
2e
• Mz+ + zH2O  M(OH)z + zH+
Fe(OH)2 + H+
Fe metal Fe metal

increases the Fe++

corrosivity of the pit

medium inside the

pits
• Aggressive anions: Halides X- ,SCN–, SO42– and ClO4–.
• Cl– is the most important anion because of its wide
spread distribution in natural water.
• Draws in chlorides and sulfates
• More of a problem in stagnant solutions.

• Very destructive since highly localized – may go

undetected until failure occurs.

• Gravity causes pit to grow downward – corrosion rate

can increase with time
 Pitting potential, Epit:
Potentiodynamic polarization Active/passive metals
Zn/NaOH

Current density
Current density

Passive metals
Al/H2SO4

Passive region Passive region

Anodic Potential Anodic Potential

Epass
Epit2 Epit1 Epit2 Epit1
Cl- aggressive anion causes pitting corrosion
At pitting potential (Epit), the current rises suddenly indicates passivity breakdown and
initiation of pitting corrosion
Epit is more negative than potential corresponding to O2 evolution reaction.
The pitting potential depends upon:
1. Concentration and nature of the aggressive anion
2. Concentration of the electrolyte
3. pH of the medium
4. Temperature
Any factor enhances pitting corrosion, shifts Epit to more negative values
 Localized corrosion:
Stress Corrosion Cracking SCC
Cracking along
Stressed CORROSIVE interagranular path
material ENVIRONMENT
(residual stress) The solution enters these
or external force cracks and causes SCC
Stress = force / cross sectional area
Examples
brasses are sensitive to ammonia

Iron or steels are sensitive to Hot,

conc. alkali or NO-3 solution.

Stainless steel are sensitive to Cl-

SCC
Factors affecting SCC:
 Specific environment
 Stress magnitude and
direction.
 Structure and metal
composition.
Localized corrosion:
Erosion Corrosion
 Erosion – corrosion is a process which
involves conjoint erosion and corrosion.
 It is a combination between corrosion and
mechanical wear on the metal surface.
 Erosion take place due to mechanical wear on
metal surface
 Corrosion takes place due to chemical or
electrochemical reactions.

 Caused by a rapid streaming liquid and the

attack is thus dependent on the degree of
turbulence.

 Erosion – corrosion can occur with most

metals, but copper is particularly sensitive.

 In many cases the attack is due to the

destruction of the protective layers or coating.
Factors affecting erosion- corrosion
 Metal surface (hardness of surface)
Soft metals are more sensitive to erosion-corrosion.
Soft metal Hard metal
Pb, Cu, Ag Cr, high carbon steel

 Environmental condition.
 High degree of turbulent:
Turbulent is formed due to high velocity of fluid and sudden change in
direction of the fluid.
As turbulent increase as mechanical wear increase and hence the
erosion will increase.
In order to decrease the turbulence effect , the thickness of tube or pipe
in the turbulence area must be increased.
 Presence of solid or suspended materials:
As suspended or solid material increase as the mechanical wear
increase and hence erosion increase