20/05/2009 corrosion 1

Corrosion
2

Corrosion is defined as the destructive and unintentional attack

of a metal

it is electrochemical and ordinarily begins at the surface.

approximately 5% of an industrialized nation’s income is spent
on corrosion and the maintenance or replacement of products
lost or contaminated as a result of corrosion reactions.

Familiar examples include the rusting of automotive body
panels and radiator and exhaust components.

Corrosion processes are occasionally used to advantage. For
example, etching procedures

corrosion 20/05/2009
 Electrochemical considerations
3

For metallic materials, the corrosion process is normally

electrochemical, that is chemical reaction in which there is
transfer of electrons from one chemical species to another.

Metal atoms characteristically lose or give up electrons in what
is called an oxidation reaction.

Hypothetical metal M that has a valence of n (or n valence
electrons) may experience oxidation according to the reaction

n+
M → M + ne −
Fe → Fe 2 + + 2 e −
Al → Al 3 + + 3 e −
The site at which oxidation takes place is called the anode
corrosion 20/05/2009
 Electrochemical considerations cont.
4

The electrons generated from each metal atom that is oxidized

must be transferred to and become a part of another chemical
species in what is termed a reduction reaction.

Example, some metals undergo corrosion in acid solutions,
which have a high concentration of hydrogen (H) ions; the H
ions are reduced as follows

2H + −
+ 2e → H 2 H 2 gas evolved

metal may be totally reduced from an ionic to a neutral
metallic state according to
n+ −
M + ne → M
That location at which reduction occurs is called the cathode
corrosion 20/05/2009
 Electrochemical considerations cont.
5

zinc will experience oxidation or

corrosion

Zn → Zn 2 + + 2 e −

The electrochemical reactions associated with the corrosion of zinc in an acid solution
Since zinc is a metal, and therefore a good electrical conductor,
these electrons may be transferred to an adjacent region at which
the H ions are reduced according to 2 H + + 2 e − → H 2 ( gas )
Total reaction: Zn → Zn 2 + + 2 e −
+
2H + 2e − → H 2
+
Zn + 2 H → Zn 2 + + H 2 ( gas ) corrosion 20/05/2009
 Electrode potentials
6

Not all metallic materials oxidize to form ions with the same
degree of ease
An electrochemical cell consisting of iron
and copper electrodes
If the iron and copper electrodes are
connected electrically, reduction will
occur for copper at the expense of the
oxidation of iron, as follows:
Fe → Fe 2 + + 2 e −
Cu + + 2 e − → cu
Cu 2 + + Fe → Cu + Fe 2 +
Cu2+ will deposit (electrodeposits) as metallic copper on the copper
electrode, while iron dissolves (corrodes) on the other side of the cell
and goes into solution.
 Electrode potentials
7

When a current passes through the external circuit, electrons

generated from the oxidation of iron flow to the copper cell in
order that Cu2+ be reduced.

In addition, there will be some net ion motion from each cell to
the other across the membrane.

This is called a galvanic couple—two metals electrically
connected in a liquid electrolyte wherein one metal becomes an
anode and corrodes, while the other acts as a cathode.

corrosion 20/05/2009
 An electrochemical cell consisting of
8
iron and zinc electrodes
galvanic couple consisting of the same iron half-
cell connected to a metal zinc electrode that is
immersed in a 1M solution

zinc is the anode and corrodes, whereas the

Fe now becomes the cathode.

Zn → Zn 2 + + 2 e −
Fe + + 2 e − → Fe
Fe 2 + + Zn → Fe + Zn 2 +

corrosion 20/05/2009
 The standard EMF series
9

These measured cell voltages

represent only differences in
electrical potential thus it is
convenient to establish a reference
point, or reference cell, to which
other cell halves may be compared.

This reference cell, arbitrarily
chosen, is the standard hydrogen
electrode

It consists of an inert platinum
electrode in a 1M H+ solutions
The standard hydrogen reference half-
cell
corrosion 20/05/2009
 The standard EMF series cont.
10

corrosion 20/05/2009
 The standard EMF series cont.
11

Consider the generalized reactions involving the oxidation of

metal M1 and the reduction of metal M2 as
n+ 0
M1 → M1 + ne − − V1
n+
M2 + ne − → M 2 + V2
0

n+ n+
M1 + M 2 → M1 +M2 ∆V 0

0 0 0
∆V = V 2 − V1
0
− V1 The standard cell potential of oxidation
0
+ V2 The standard cell potential of reduction
0
∆V The overall cell potential
corrosion 20/05/2009
 Concentration and temperature on cell
potential
12

The cell potential is highly dependent on concentration and

temperature.

If M1 and M2 electrodes are pure metals, the cell potential
depends on the absolute temperature T and the molar ion
concentrations [M1n+ ] and [M2n+ ] according to the Nernst
equation:

∆V 0 0
= V 2 − V1
0
−
RT
ln
M1 [ n+
]
R is the gas constant,
nf M2 [
n+
]
n is the number of electrons participating in either of the
half-cell reactions,
F is the Faraday constant, 96,500 C/mol
corrosion 20/05/2009
 Concentration and temperature on
13
cell potential cont.

At 25oC (about room temperature) Nernst equation will be
simplified as:

0
∆ V = V2
0 0
− V1 −
0 .0592
log
M1 [ n+
]
n M2
n+
[ ]

corrosion 20/05/2009
 Corrosion penetration rate (CPR),
14

 It is the rate of material removal as a consequence of the

chemical action given by:
K Constant
KW
CPR = W Weight loss with exposure time t
ρ At ρ Density
A Area exposed
 If there is an electric current associated with electrochemical
corrosion reactions CPR will become:
i r Rate
r= i Current density(current/Area)
nf
n Number of electrons
f Faraday's constant (96500 c/mol)

corrosion 20/05/2009
 Prediction of corrosion rates
15

 Polarization Consider the standard Zn/H2 electrochemical cell

shown in Figure.

The potentials of the two electrodes will not be at
the values determined from EMF series because
the system is now a nonequilibrium one.

The displacement of each electrode potential from
its equilibrium value is termed polarization, and
the magnitude of this displacement is the
overvoltage (η )

Suppose that the zinc electrode in Figure above has a potential of

0.621 V after it has been connected to the platinum electrode. The equilibrium
potential is 0.763 V (Table EMF), and, therefore the overvoltage
η = − 0 . 621 − ( − 0 . 763 ) = + 0 . 142 V corrosion 20/05/2009
 Activation polarization
16
It is the condition wherein the reaction rate is controlled by the
one step in the series that occurs at the slowest rate.

1. Adsorption of H ions from the

solution onto the zinc surface.
2. Electron transfer from the zinc to
form a hydrogen atom,
+
H + e− → H
3. Combining of two hydrogen atoms
to form a molecule of hydrogen,
2H → H 2
4. The coalescence of many
hydrogen molecules to form a
bubble. corrosion 20/05/2009
 Activation polarization for Hydrogen
17
electrode
The activation polarization overvoltage
is given by: η a = ± β log i
i0
β Constants for a particular
i0 Half cell

2H +
+ 2e − → H 2 rred

H 2 → 2H +
+ 2e − roxid

The exchange current density is determined from; rred = roxid

i0
rred = roxid = r0 = the exchange current density
nf corrosion 20/05/2009
 Corrosion of zinc in acidic solution
18
Zn → Zn 2 + + 2 e −
2 H + + 2e − → H 2
+
Zn + 2 H → Zn 2 + + H 2 ( gas )

Hydrogen and zinc experience activation

polarization along their respective lines.
Corrosion potential, designated VC,
occurs when oxidation and reduction
rates are equal and the corresponding
corrosion current density iC.
The corrosion rate of zinc (which also
corresponds to the rate of hydrogen
evolution) may thus be computed by
insertion of this iC value into: i
r =
corrosion 20/05/2009 nf
Activation polarization of both cells
 Example
19

Zinc experiences corrosion in an acid solution according to the

reaction
Zn + 2 H + → Zn 2 + + H 2 ( gas )
The rate of both oxidation and reduction half-reactions are
controlled by activation polarization
Compute the rate of oxidation of Zn(in mol/cm2-s) given the
following activation polarization data
For Zn For Hydrogen
V(Zn/Zn 2+) = -0.763 V(H+/H) = 0V
i0=10-7 A/cm2 i0=10-10 A/cm2
β=+0.09 β=-0.08

corrosion 20/05/2009
 Ex. Zinc corrosion cont.
20

The reduction potential is:

 [i ] 
VH = V(H + / H ) + β H log  
 [i0 H ] 
2

The oxidation potential is:

 [i ] 
VZn = V(Zn / Zn 2+ ) + β Zn log  
 [i0 Zn ] 
Setting VH = VZn
 [i ]   [i] 
V(H + / H ) + β H log  2+ + βZn log 
 = V
 [i0 H ] 
( ) 
 [i0Zn ] 
2 Zn/ Zn

corrosion 20/05/2009
 Ex. Zinc corrosion cont.
21

Solving for log i i.e log ic

 
log ic = 
1
[
 V(H / H ) − V(Zn / Zn ) − β H log i0 H + β Zn log i0 Zn
+ 2+ ]
 β Zn − β H 
log ic = −3.924 ic = 10 −3.924 = 1.19 × 10 −4 A / cm 2

i 1 . 19 × 10 − 4
r = = = 6 . 17 × 10 −10 A / cm 2 − s
nf 2 × 96500
corrosion potential VC = VH = VZn
 [i ] 
Vc = V(H + / H ) + β H log  
 [i0 H ] 
2

VC = −0.486
corrosion 20/05/2009
 Forms of corrosion
22

Inter granular
corrosion Selective
Pitting leaching

Crevice Erosion
corrosion corrosion

Galvanic Stress
corrosion corrosion

Uniform Forms of Hydrogen

attack Corrosion Embrittlement

corrosion 20/05/2009
 Uniform attack
23

Uniform attack is a form of electrochemical corrosion that

occurs with equivalent intensity over the entire exposed surface
and often leaves behind a scale or deposit.

In a microscopic sense, the oxidation and reduction reactions

occur randomly over the surface.

Some familiar examples include general rusting of steel and iron

and the tarnishing of silverware.

corrosion 20/05/2009
 Galvanic corrosion
24

 It occurs when two metals or alloys having different

compositions are electrically coupled while exposed to
an electrolyte.
 The less noble or more reactive metal in the particular
environment will experience corrosion
 the more inert metal, the cathode, will be protected
from corrosion.
 For example, steel screws corrode when in contact with
brass in a marine environment
 if copper and steel tubing are joined in a domestic
water heater, the steel will corrode in the vicinity of the
junction.
corrosion 20/05/2009
 Galvanic corrosion cont.
25

magnesium The rate of galvanic attack depends on

the relative anode-to-cathode surface
areas that are exposed to the
electrolyte,
steel the rate is related directly to the
cathode–anode area ratio; that is, for a
given cathode area, a smaller anode
will corrode more rapidly than a larger
one.
The reason for high corrosion for small
anode is that corrosion rate depends on
Galvanic corrosion of a
current density
magnesium shell that was cast
around a steel core. corrosion 20/05/2009
 Measures to reduce Galvanic
26
corrosion
a) If coupling of dissimilar metals is necessary, choose two that
are close together in the galvanic series.

b) Avoid an unfavorable anode-to-cathode surface area ratio;

use an anode area as large as possible.

c) Electrically insulate dissimilar metals from each other.

d) Electrically connect a third, anodic metal to the other two;

this is a form of cathodic protection,.

corrosion 20/05/2009
 Crevice corrosion
27

It is caused by concentration differences of ions or dissolved

gases in the electrolyte solution, and between two regions of
the same metal piece.

A good example of this type of corrosion occurs under
deposits of dirt or corrosion products where the solution
becomes stagnant and there is localized depletion of dissolved
oxygen.

corrosion 20/05/2009
 Mechanisms of Crevice corrosion
28

Schematic illustration of
the mechanism of crevice
corrosion between two
riveted sheets

o After oxygen has been depleted within the crevice, oxidation of

the metal occurs at this position according to: M → M n + + ne −
oElectrons from this electrochemical reaction are conducted through
the metal to adjacent external regions, where they consumed by
reduction corrosion 20/05/2009
 Pitting
29

Pitting is another form of very localized corrosion attack

in which small pits or holes form.

They ordinarily penetrate from the top of a horizontal
surface downward in a nearly vertical direction.

The mechanism for pitting is probably the same as for
crevice corrosion in that oxidation occurs within the pit
itself, with complementary reduction at the surface.

A pit may be initiated by a localized surface defect such
as a scratch or a slight variation in compositions.

corrosion 20/05/2009
 Pitting cont.
30

specimens having polished surfaces display a greater

resistance to pitting corrosion.

Stainless steels are somewhat susceptible to this form of
corrosion; however, alloying with about 2% molybdenum
enhances their resistance significantly.

The pitting of a 304 stainless

steel plate by an acid-chloride
solution.

corrosion 20/05/2009
 Intergranular corrosion
31

chromium carbide particles that have

precipitated along grain boundaries in
stainless steel, and the attendant zones
of chromium depletion

It occurs preferentially along grain boundaries

The net result is that a macroscopic specimen disintegrates along its
grain boundaries.

High temperature sensitized to intergranular attack.

heat treatment permits the formation of small precipitate particles of
chromium carbide (Cr23C6) by reaction between the chromium and
carbon in the stainless steel
corrosion 20/05/2009
 Intergranular corrosion
32

Intergranular corrosion is an especially severe problem in the

welding of stainless steels, when it is often termed weld decay
Intergranular corrosion in stainless steel can
be minimized by:
(1)subjecting the sensitized material to a high-
temperature heat treatment in which all the
chromium carbide particles are
redissolved,
(2) lowering the carbon content below 0.03
wt% C so that carbide formation is
minimal,
(3)alloying the stainless steel with another
metal such as niobium or titanium
corrosion 20/05/2009
 Selective leaching
33

Selective leaching is found in solid solution alloys and occurs when

one element or constituent is preferentially removed as a
consequence of corrosion processes.

The most common example is the dezincification of brass, in which
zinc is selectively leached from a copper–zinc brass alloy.
 The mechanical properties of the alloy are significantly impaired, since
only a porous mass of copper remains
 material changes from yellow to a red or copper color.

It can also occur with other alloy systems in which aluminum, iron,
cobalt, chromium, and other elements are vulnerable to
preferential removal.

corrosion 20/05/2009
 Erosion–Corrosion
34

Erosion–corrosion arises from the combined action of chemical

attack and mechanical abrasion or wear as a consequence of
fluid motion.

all metal alloys, to one degree or another, are susceptible to
erosion–corrosion.

The nature of the fluid can have a dramatic influence on the
corrosion behavior.

Increasing fluid velocity normally enhances the rate of
corrosion

corrosion 20/05/2009
 Erosion–Corrosion cont.
35

 Erosion–corrosion is commonly found in piping, especially at

bends, elbows,and abrupt changes in pipe diameter—positions
where the fluid changes direction or flow suddenly becomes
turbulent. Ex. Propellers, turbine blades, valves, and pumps are
also susceptible to this form of corrosion

Impingement failure of an elbow

that was part of a steam condensate line

corrosion 20/05/2009
 Stress corrosion
36

Stress corrosion, sometimes termed stress corrosion cracking,

results from the combined action of an applied tensile stress
and a corrosive environment; both influences are necessary.

Most alloys are susceptible to stress corrosion in specific
environments, especially at moderate stress levels
 most stainless steels stress corrode in solutions containing chloride
ions,
 brasses are especially vulnerable when exposed to ammonia

corrosion 20/05/2009
 Stress corrosion cont.
37

Photomicrograph showing intergranular

stress corrosion cracking in brass
Measure to take in reducing or eliminating stress corrosion is :

lower the magnitude of the stress by reducing the external load or
increasing the cross-sectional area perpendicular to the applied stress.

appropriate heat treatment may be used to anneal out any residual
thermal stresses.
corrosion 20/05/2009
 Hydrogen Embrittlement
38

Hydrogen embrittlement is similar to stress corrosion

It is the penetration of atomic hydrogen (H) into the material
which reduces the strength and ductility of a material

the terms hydrogen induced cracking and hydrogen stress
cracking are sometimes also used

In order for hydrogen embrittlement to occur, some source of
hydrogen must be present,

High-strength steels are susceptible to hydrogen embrittlement,
and increasing strength tends to enhance the material’s
susceptibility

corrosion 20/05/2009
 Hydrogen Embrittlement cont.
39

Techniques commonly used to reduce the likelihood of hydrogen

embrittlement include:

reducing the tensile strength of the alloy via a heat treatment;

removal of the source of hydrogen; ‘‘baking’’ the alloy at an

elevated temperature

to drive out any dissolved hydrogen; and substitution of a more

embrittlementresistant alloy.

corrosion 20/05/2009
 Corrosion prevention
40

corrosion 20/05/2009
 Cathodic protection
41

Cathodic protection simply involves supplying, from an external

source, electrons to the metal to be protected, making it a
cathode

cathodic protection technique employs a galvanic couple: the
metal to be protected is electrically connected to another
metal that is more reactive in the particular environment. The
latter experiences oxidation, and, upon giving up
electrons,protects the first metal from corrosion.

The oxidized metal is often called a sacrificial anode.

magnesium and zinc are commonly used as such because they
lie at the anodic end of the galvanic series

corrosion 20/05/2009
 Cathodic protection cont.
42

An underground pipeline using a magnesium sacrificial

anode
corrosion 20/05/2009
 Cathodic protection cont.
43

An underground tank using an impressed current

The negative terminal of the power source is connected
to the structure to be protected.
 The other terminal is joined to an inert anode (often graphite), which
is, in this case, buried in the soil; high-conductivity backfill material
provides good electrical contact betweencorrosion
the anode and surrounding
20/05/2009
soil
 Cathodic protection cont.
44

process of galvanizing is simply one in

which a layer of zinc is applied to the
surface of steel by hot dipping.

corrosion of the zinc coating will proceed

at an extremely slow rate because the
ratio of the anode-to-cathode surface
area is quite large.

Galvanic protection of steel as provided by a coating of zinc

20/05/2009
 Oxidation
45

Gaseous atmosphere Produces oxide

layer
M + 1 2 O2 → MO
M2+ ions must diffuse away from the
metal–scale
interface, and/or O2- ions must
diffuse toward this same interface

The oxide scale serves both as an electrolyte and electrical
circuit for the passage of electrons.

protect the metal from rapid oxidation when it acts as a barrier to
ionic diffusion and/or electrical conduction;
corrosion 20/05/2009