1

ENVIORNMENTAL DEGRADATION OF MATERIALS 2013

A compilation from literature by Dr. Balakrishna Palanki
palankibalakrishna@yahoo.com


Mighty ships upon the ocean
suffer from severe corrosion.
Even those that stay at dockside
are rapidly becoming oxide
Alas, that piling in the sea
is mostly Fe
2
O
3
.
And when the ocean meets the shore
Youll find theres Fe
3
O
4
,
cause when the wind is salt and gusty
things are getting awful rusty.
- T.R.B. WATSON


1. Basics of Corrosion Science and Engineering

Metals are valuable to man due to their useful properties such as strength and
formability. Unfortunately, metals are unstable and easily combine with other
elements to form compounds. For this reason, in nature, most metals occur in the
form of compounds as minerals. For example, the metal Al occurs in the form of
Al
2
O
3
. Cu exists as carbonate or sulphide. Just as work has to be done to pump water
to a higher level, work has to be done to extract a metal from its mineral. On the other
hand, just as water flows naturally from a higher to a lower level, the corrosion of a
metal is a spontaneous process. The metal would like to go back to its combined form
by way of corrosion. Fe rusts by forming oxide, silver stains by reacting with sulphur
in the environment and copper statues form patina of green carbonate. Hence
corrosion is extractive metallurgy in reverse. Corrosion may be defined as the
degradation of a material (metal, ceramic, polymer or composite) caused by its
unintentional chemical or electrochemical interaction with environment, starting at
its surface. Corrosion is a progressive oxidation reaction balanced by a
corresponding reduction reaction. Combustion of a metal powder is not considered as
corrosion. Corrosion increases with exposure time, temperature and environmental
and several other factors. Only iron and steel rust. Other metals corrode!

1.1. Corrosion of iron

The importance of iron is seen from the fact that the quantity of iron used in the world
is 7 times that of all other metals put together. The corrosion (oxidation) of iron in
acids yields soluble salts and hydrogen gas and can be expressed as half reactions:

Fe Fe
++
+ 2e
2 H
+
+ 2 e H
2


In the above the oxidation of Fe to Fe
++
is balanced by the reduction of H
+
to H
2
gas.


2

The term OILRIG indicates that Oxidation is Loss of electrons and Reduction is Gain
of Electrons.
The half reactions may be combined as below:

Fe + 2 H
+
= Fe
++
+ H
2


The corrosion of metals can also occur in fresh water, seawater, salt solutions, and
alkaline or basic media. In almost all of these environments, corrosion occurs
importantly only if dissolved oxygen is also present. Water solutions rapidly
dissolve oxygen from the air, and this is the source of the oxygen required in the
corrosion process. The most familiar corrosion of this type is the rusting of iron when
exposed to a moist atmosphere.
Fe Fe
++
+ 2e
O
2
+ H
2
O + 2 e 2 OH
-


The half reaction above may be combined to get

4 Fe + 6 H
2
O + 3 O
2
4 Fe(OH)
2

In this equation, iron combines with water and oxygen to produce an insoluble
reddish-brown corrosion product that falls out of the solution, as shown by the
downward pointing arrow.
During rusting in the atmosphere, there is an opportunity for drying, and this ferric
hydroxide dehydrates and forms the familiar red-brown ferric oxide (rust) or Fe
2
O
3
, as
shown below:
2 Fe(OH)
3
Fe
2
O
3
+ 3 H
2
O

Experiment to demonstrate the importance of water and oxygen in corrosion:
Take three test tubes A, B and C. Keep one clean nail in each. Leave A sealed with a
cork only with air, using anhydrous calcium chloride at the bottom as dessicant to
keep air dry. Pour water in B to partly submerge the nail and seal In C, submerge the
nail fully in distilled water, pour oil (which floats on the water) to prevent ingress of
air into water and seal the tube. After a few days, only the nail in B is found to show
rust. Corrosion of iron or steel can be prevented by removing contact with air and
moisture.


1.2 Metal electrodes

When a metal is placed in its solution, a small part of the metal dissolves or ionises
and the metal ions (which no longer have metallic properties) join the solution. This
process of ionization leaves a negative charge on the metal. The left over negative
charge in the metal gives the metal a potential.

The transfer of the metal from the metal into its solution is called oxidation or
corrosion. Oxidation liberates electrons.

3
M M
+
+ e

or

M M
++
+ 2e

The number of electrons released into the metal depends on its valency. It is usually
denoted by the letter z. z is 1, 2 or 3 etc. The place where oxidation or corrosion takes
place is called the anode.

Soon the reverse reaction begins.

M
+
+ e M

The reverse reaction s called reduction. Reduction consumes electrons. The place
where reduction takes place is called cathode. The rate of oxidation and the rate of
reduction become equal. We say that dynamic equilibrium has been reached. It is the
lowest free energy state of the reaction. At equilibrium, the system is stable and there
is no driving force for any change from that state. When there is no net reaction, that
is, when the equilibrium is reached, the potential displayed by the metal is called
equilibrium electrode potential. If you increase the potential by some means, more
oxidation will take place. If you decrease the potential by some means, more
reduction will take place.

The tendency to oxidise is not the same for different metals. Some metals tend to
oxidise readily, while some are reluctant to oxidise. The metals that oxidise readily
are called base metals. For example, you can not hold a piece of sodium in your hand.
It burns instantly. Some other metals like calcium or magnesium readily react with
water. Some other metals such as iron or zinc react with acid. On the other hand, there
are metals like gold which do not react readily. Such metals are called Noble metals.
Noble metals as well as base metals all exhibit a potential when in contact with their
solution, though the tendency to oxidise are different. Based on their reactivity, the
metals can be arranged in an order.

The equilibrium potential exhibited by a metal in contact with its solution when the
conditions are standard, is called standard electrode potential. By standard conditions,
we mean a temperature of 25 C (298 K), a pressure of one atm and a pH of zero or a
solution strength of one molarity. Metals arranged in the order of the standard
electrode potentials are called the electromotive or emf series. The series has base
metals at one end and noble metals at the other end.

A potential can not be measured in absolute terms. It can be measured as a potential
difference. Just as you take mean sea level as zero and measure heights relative to it,
we take the hydrogen gas hydrogen ion equilibrium under standard conditions to be
zero volts and measure potentials of all other metals relative to it.

2 H
+
+ 2 e H
2
Zero volts.

The above equation is the same as

4
H
+
+ e (1/2) H
2
Zero volts.
pH is defined as
pH = - log [H
+
]

When [H
+
] is one mole per litre of the solution, log [H
+
] is zero.

The reference electrode, which is used for potential measurements, is called the
standard hydrogen electrode or SHE, the potential of which has been taken to be 0 V.

Zn Zn
+
+ e has a standard electrode potential of minus 0.76 volts.

Cu Cu
++
+ 2e has a standard electrode potential of plus 0.334 volts.

Suppose one wishes to measure the heights of poles in a field, and he is not able to see
the ground level, because of tall grass. Still, he can measure the heights by taking the
tip of one pole to be at a height of zero meters. Then he measures the heights of the
tips of other poles relative to this. Then the poles shorter than the standard pole will
have negative heights. The poles longer than the standard pole will have positive
heights.

The standard hydrogen electrode is analogous to the standard pole above.

Reactions such as Zn Zn
++
+ 2e or

2 H
+
+ 2 e H
2
are called Half reactions.

In contrast, a reaction such as

Zn + 2 H
+
Zn
++
+ H
2
is a full reaction, the half reactions of which are as above.
The full reaction is obtained by adding the half reactions. The potential of the full
reaction is also the addition of the potentials of the half reactions.

In real situations, there are no half reactions. All are full reactions. One type of half
reaction is balanced by another type of half reaction. For example, oxidation half
reaction has to be balanced by a reduction half reaction. This is because electric
charge has to be conserved.

1.3 Nernst Equation

The potential of a metal in contact with its solution can be changed by changing the
concentration, pressure or temperature. The way a potential changes when these are
changed is expressed as Nernst equation.
To determine the potential of a system in which the reactants are not at unit activity,
Nernst Equation is employed. For the chemical equation represented by

A + B = C + D


B A
D C
H
a a
a a
zF
RT
E E ln
0

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which is the same as

D C
B A
H
a a
a a
zF
RT
E E ln
0


where E
H
is the cell potential, E
0
the standard cell potential, R is the gas constant, T is
the absolute temperature, z is the number of electrons transferred, F is the Faraday
Constant, a
A
, a
B
etc are the activities (concentrations) of the species. Both E
0
and E
H

are equilibrium potentials.

Converting log to the base 10,

B A
D C
H
a a
a a
zF
RT
E E log 3 . 2
0


At 25C, and substituting F by 96485 coulombs, R by 8.314 J.mol
-1
.K
-1


B A
D C
H
a a
a a
z
E E log
0592 . 0
0


For the half reaction Zn Zn
+
+ e, z = 1
For the half reaction, Cu Cu
++
+ 2e, z = 2

We have seen how the potential can by increased or decreased by changing
temperature, pressure or concentration. There are other important ways of changing
the potential.

One way is to connect the metal to a more noble metal. For example, you can connect
zinc electrode with a copper electrode. The potential of the zinc electrode increases
from minus 0.76 volts to a greater value. The potential of the copper decreases from
plus 0.334 volts to a lesser value.
Since the potential of zinc has been increased (by connecting to copper),
oxidation rate of zinc increases. Since the potential of copper has been decreased (by
connecting to zinc), the reduction rate of copper increases. When the copper and zinc
remain connected electrolytically, the zinc corrodes rapidly. The oxidation half
reaction of zinc is balanced by the reduction half reaction of copper.

1.4 Electrolyte and Electrolytic cell

An electrolyte is a solution containing positive and negatively charged ions. For
example, an electrolytic solution of NaCl consists of Na
+
and Cl
-
ions, in water. The
electrolyte is usually an aqueous solution. Molten salts not containing water are also
electrolytes. An electrolytic cell is a combination of an anode and a cathode, both
immersed in an electrolyte. The anode and cathode may not be connected to each
other, or may be connected to a load or may be shorted. On this basis, three types of
electrolytic cells are described below.
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When the electrodes are not in contact with each other, the electrolytic cell is
called battery ( a dc power source) and can be used for supplying electrical energy to
a load, such as a torch light or engine starter in an automobile. When a dc power
source is connected to an electrolytic cell, electrolysis or electroplating takes place.
Electro forming and elctrowinning are also achieved by connecting a dc power
source to the electrolytic cell. Electrolysis of water yields hydrogen gas at the cathode
and oxygen gas at the anode. When the electrodes of electrolytic cells are joined
together by a conducting wire, it becomes a corrosion cell. A short circuited
electrolytic cell is a corrosion cell. Zinc and copper in their solutions and connected
by a conducting wire form a corrosion cell, where the zinc undergoes oxidation and
copper undergoes reduction. The electrons released by zinc changing to zinc ions are
taken up by copper ions to become copper metal. The oxidation reaction of zinc is
balanced by the reduction reaction of copper. In other words, zinc corrodes and
protects the copper.
It is possible to change the potential of the copper and zinc simply by connecting
them. It is also possible to change the potential by connecting to the pole of a battery
or dc power source. If you connect the metal to the positive pole, the potential of the
metal increases and oxidation of the metal increases. If you connect it to the negative
pole, reduction of the metal increases.

When the potential is changed, we say that there is polarisation. Polarisation is the
difference between actual applied voltage and the equilibrium potential. When the
potential is at equilibrium value, there is no net oxidation or net reduction. When the
potential is changed, there is an increase in oxidation or reduction rates. The excess
potential or the overvoltage is related to the consequent current by Tafel Law.

1.5 Corrosion reactions

The corrosion of a metal which is an oxidation process taking place at the anode may
be represented by the half reaction:

Zn Zn
++
+ 2e or

Fe Fe
++
+ 2e

Cu Cu
++
+ 2e

For corrosion to be possible, the above half reactions taking place at the anode need to
be necessarily balanced by one or more reduction half reactions taking place at the
cathode. Electric charge can not be accumulated and has to be conserved. In other
words, the electrons released by the anodic oxidation half reaction travel through the
conducting wire, reach the cathode and get consumed in the cathodic reduction half
reaction. Note that ions travel through the electrolyte, constituting an ionic current,
while electrons travel through the metal constituting an electronic current.

Some common cathodic reduction half reactions responsible for causing corrosion of
a metal are given below:

In acidic solutions, with no oxygen present 2 H
+
+ 2 e H
2


7
In acidic solutions, with oxygen present O
2
+ 2 H
+
+ 2 e H
2
O

In neutral or alkaline solutions O
2
+ H
2
O + 2 e 2 OH
-


The reduction of another metal ion may also serve as a balancing half reaction:

Cu
++
+ 2e Cu

2. Thermodynamics of Corrosion

2.1 Energy can neither be created nor destroyed.
All spontaneous changes occur with a release of free energy from the system to the
surroundings at constant temperature and pressure. In nature, water runs downhill, hot
coffee goes cold and spinning tops slow down. Work has to be performed for
achieving changes that are not spontaneous. Corrosion is a spontaneous
electrochemical process, where free energy is released and the metal returned to its
stable (combined) state. The driving force for corrosion reaction is chemical energy,
energy stored in chemical bonds of substances or internal energy. Free energy is the
portion of internal energy available for powering engines or causing corrosion
reaction. We can force an electrochemical reaction to proceed in the reverse direction
by connecting a source of current to the electrodes, as in electroplating or electro-
winning.

2.2 Electrolysis of water

In the electrolysis of water, hydrogen gas is evolved at the cathode and oxygen gas is
evolved at the anode. Electrolysis of water takes place when the applied voltage
exceeds 1.2 V as per the following equations:

At the anode: H
2
O = O
2
+ 2 H
+
+ 2 e (E
0
= 1.23 V)

At the cathode: 2 H
+
+ 2 e = H
2
(pH < 7) (E
0
= 0 V)

The electrons released by the anodic reaction are consumed by the cathodic reaction.
Note that other anodic reactions are possible, with other values of equilibrium
potentials. Correspondingly, the electrolytic voltage requirement also changes.

The potential of a metal in contact with its solution M = M
++
+ 2e is given by the
Nernst equation:

E = E
0
- 2.303 [RT/(nF)] log (M
+
/M)

In the case of hydrogen gas and hydrogen ions, for the equilibrium represented by

2 H
+
+ 2 e = H
2
(pH < 7) (E
0
= 0 V)

the Nernst equation may be written as

E = E
0
- 2.303 [RT/(nF)] log [1/(H
+
)]

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At a temperature of 25 C, E
0
has the value zero and 2.303 [RT/(zF) has the value
0.059
E = 0.059 log (H
+
)

By definition, pH = - log (H
+
)

E = - 0.059 pH

This is the equation of a straight line, with negative slope.

If the potential is smaller than that indicated in the above expression, hydrogen gas
evolves.


In the case of oxygen gas and oxygen ions,

O
2
+ 2 H
+
+ 2 e = H
2
O (E
0
= 1.23 V)


the equation becomes

E = 1.23 + 0.059 log (H
+
)

E = 1.23 - 0.059 pH

This is the equation of a straight line, parallel to the hydrogen gas / hydrogen ion
equilibrium line.

If the potential is larger than that indicated in the above expression, oxygen gas
evolves. Thus, for the electrolysis of water, the potential difference should therefore
be at least 1.23 volts.

Note that the equilibrium potential becomes the standard equilibrium potential when
pH = 0.

2.3 Pourbaix Diagrams:

The application of thermodynamics to corrosion phenomena have been generalized by
means of potential pH plots. These are called Pourbaix diagrams, after Dr. Marcel
Pourbaix who first suggested their use. Such diagrams are constructed from
calculations based on the Nernst equation and solubility data for various compounds.
In the diagram for iron, for example, it is possible to delineate areas in which iron,
iron hydroxide, ferrous ions, etc., are thermodynamically stable. That is, these forms
represent states of lowest free energy.

The main uses of these diagrams are (1) predicting the spontaneous direction of
reactions, (2) estimating the composition of corrosion products, and (3) predicting
environmental changes that will prevent or reduce corrosive attack. For example, the
large region labeled Fe indicates that iron is inert under these conditions of potential
and pH.
9

The electromotive series only takes into account, those electrochemical equilibria
involving metals and their simple cations (M
z+
), in other words, the only type of
reaction considered is

M = M
z+
+ 2 e

which only contains e terms in addition to the metal and metal ion and so is only
potential dependent. There are several other relevant reactions such as

M + z H
2
O = M(OH)
z
+ z H
+
+ 2 e

in which the metal hydroxide can represent a protective film if it is closely packed,
tightly adherent and has a sufficiently low solubility. Another reaction is

M + 2z (OH) = MO
2

z-
+ z H
2
O + 2 e

which represents corrosion of the metal in an alkaline medium. These equilibria are
potential and pH dependent due to the presence of e, H
+
or OH
-
. Reactions dependent
only on pH can also occur:

M
z+
+ z (OH
-
) = M(OH)
z

MO
z
z-
+ z H
+
= M(OH)
z

The line a-b in the figure represents the hydrogen-hydrogen ion equilibrium. E
H
= E
0

= 0 when pH = 1. If a point is below the line a-b, the reaction proceeds from left to
right i.e., H
2
evolves. If it is above the line, H
2
ionises till equilibrium is reached.
Similarly when the point (E
H
, pH) is above c-d, O
2
evolution is possible.

If a potential difference of 1.2 volts is maintained between the electrodes, at the anode
H
2
O = O
2
+ 2 H
+
+ 2 e and at the cathode 2 H
+
+ 2 e = H
2
.

All metals corrode, though the rates and extents vary. As corrosion proceeds, the
concentration of metal ions increases. If the equilibrium concentration of the ions is
small (10
-6
gram ions/litre), the metal is taken to be immune to corrosion and the lines
in the E
H
- pH diagram are drawn for this concentration.

1. Fe = Fe
++
+ 2e

2. Fe
++
= Fe
+++
+ e

3. Fe
++
+ 3 (OH
-
) = Fe(OH)
3
+ e

4. Fe
+++
+ 3 H
2
O = Fe(OH)
3
+ 3H
+


5. Fe + 3 H
2
O = Fe(OH)
3
+ 3H
+
+ 3e

6. Fe + 2 H
2
O = FeO
2
H
-
+ 3H
+
+ 2e

7. FeO
2
H
-
+ H
2
O = Fe(OH)
3
+ e
10

Limitations: The thermodynamic approach excludes kinetic data. Only those
equilibria concerned with metal in conjunction with water are used in constructing E
H

- pH diagrams so that only OH
-
is considered as the precipitating or complexing ion.
In practical corrosion, there are Cl
-
, SO
4
=
, PO
4
=
etc.


2.4 Passivity

Metals that normally fall victim to corrosion will sometimes exhibit a passivity to
corrosion. Passivity is a phenomenon in which a metal (or alloy) exhibits a much
higher corrosion resistance than its position in the electrochemical series would
indicate. This happens when the initial corrosion product, if tenacious and nonporous,
actually shields the metal against further corrosion. Iron corrodes (dissolves) in dilute
nitric acid but not in concentrated acid due to passivation. Aluminium, chromium and
zirconium which are at the base end of the electrochemical series, display excellent
corrosion resistance because the initial oxide films formed (Al
2
O
3
, Cr
2
O
3,
ZrO
2
)
protect the metal from further attack. Chromium used as alloying element in SS
behaves the same way. Passivity is the characteristic of a metal exhibited when the
metal does not become active in the corrosion reaction. Passivity is caused by the
build up of a stable tenacious layer of metal oxide on the surface of the metal. This
oxide layer is formed by corrosion on a clean metal surface, where the corrosion
products are insoluble in the particular environment to which the metal is exposed.
Once the layer, or film, is formed, it acts as a barrier separating the metal surface from
the environment. For further corrosion to occur, the reactants must diffuse through
the oxide film. Such diffusion is very slow or non-existent, thus corrosion either
decreases markedly or stops. Metals such as zirconium, chromium, aluminum and the
stainless steel form thin, tenacious oxide films when exposed to the atmosphere or to
pure water at room temperature. In some cases, the film is extremely thin and may be
invisible to the unaided eye, but it is still very effective in giving these metals a
marked passivity.

2.4 The Pilling Bedworth Ratio

If the volume of the scale produced is greater than the volume of metal ionised in
producing it, the scale tends to be formed in lateral compression, and can be compact
and protective assuming the compressive forces are not so great to disrupt it. On the
other hand, if the volume of scale is less than the volume of metal ionised in
producing it, the scale tends to be formed in lateral tension, and since most scales are
not mechanically strong in tension it will probably be cracked and crazed, thus
affording incomplete coverage of the metal and therefore be nonprotective.

Molecular weight of the scale > Molecular weight of the metal
Density of the scale Density of the metal

(M/D) > (m / d) Or (Md / Dm) > 1 for scale to form in compression

For Al Al
2
O
3
the ratio is 1.275 so the scale will be formed in compression. In
general, metals with volume ratios of less than 1 form nonprotective oxides, as do
those with very high volume ratios (2 to 3), but this ratio was intended only as an
11
empirical criterion and does not encompass other properties more important in
determining oxidation resistance. To be protective to oxygen reaction, an oxide must
possess good adherence, a high melting point, a low vapour pressure, good high
temperature plasticity to resist fracture, and low electrical conductivity or low
diffusion coefficients for metal ions and oxygen. For cyclic temperatures, the metal
and oxide should possess similar coefficients of expansion.

So far it has been assumed that when a corrosion reaction is balanced by a reduction
reaction both the anode and the cathode are polarised to the same potential E
corr
. In
practice, there is IR drop due to the resistance of the metal & electrolyte.


oxygen evolution
and acidification
hydrogen evolution
and alkalization
water thermodynamically stable
12



13



3. Kinetics of Corrosion

3.1 The Faraday

From Faradays laws of electrolysis it is known that the mass of a substance liberated,
deposited or dissolved in any electrochemical reaction is proportional to the charge or
current multiplied by time.

dm = I dt

where dm is the mass involved, I is the current and dt is the time.

Valency is a measure of the combining power of an atom. Gram equivalent for acids
means the amount of material capable of releasing one gram ion hydrogen ions. For
example for HCl, it is the same as molecular weight, 36.5 g and for H
2
SO
4
; it is half
the molecule weight i.e. 49 g.

Consider M M
++
+ 2 e

6 x 10
23
correspond to
Atoms of M 2 x 6 x 10
23
electrons

or

1 gm atom 2 x 6 x 10
23
x 1.6 x 10
-19
coulombs
( or 2 gm equivalents in this case)

1 gm equivalent 6 x 10
23
x 1.6 x 10
-19
coulombs

96487 coulombs (1 faraday)


3.2 Corrosion current as a measure of corrosion rate

Corrosion rate may be measured as thickness loss or weight loss per unit time per unit
area. It may also be measured using current density.

14
From Faradays first law of electrolysis it is known that the mass of a substance
liberated, deposited or dissolved in any electrochemical reaction is proportional to the
charge or current multiplied by time.

dm I dt

where dm is the mass involved, I is the current and dt is the time.

According to the first law of Faraday, the rate of a reaction can be measured by the
current density. Current density is denoted by the small i.

Mass per unit time (dm/dt) current ( I )
Mass per unit area per unit time current density ( i )

According to Faradays second law, for the same charge, the mass deposited is
proportional to the equivalent weight of the element.


3.3 Dissimilar Metal Coupling Effect:

The more active metal will become the anode of the couple in a wet corrosion cell.
The more noble metal will become the cathode of the couple in a wet corrosion cell.
The corrosion rate of the more active metal will be accelerated, while that of the more
noble metal is retarded (the cathode may still corrode, depending upon the magnitude
of the cathodic polarization induced by coupling of the more reactive metal).


3.4 Corrosion Rate, Temperature Effect
The order of galvanic series may reverse under certain circumstances, for example,
Zn and Fe at elevated temperatures in some potable water systems. Like most other
chemical reactions, corrosion rates increase as temperature increases. Temperature
and pressure of the medium govern the solubilities of the corrosive species in the
fluid, such as oxygen (O
2
), carbon dioxide (C0
2
), chlorides, and hydroxides. A rule of
thumb is that the reaction rate doubles with a 20F to 50F temperature rise. This
linear increase with temperature does not continue indefinitely due, in part, to a
change in the oxide film. The environment plays an important role in a corrosion
process. Corrosion rates in tropical countries and seaside places are higher than in
cold countries and inland places.

3.5 Corrosion rate, other effects

Cathode to anode area ratio: Greater area ratio will result in a greater accelerating
factor in the rate of galvanic corrosion
Velocity effect: When water velocity is extremely high, the impact of the water tends
to remove the protective oxide layer and some of the metal under it (erosion), thus,
exposing more metal to corrosion. Water velocities of 30 to 40 ft per second are
usually considered to cause erosion.

15
Composition Increasing concentration of corrosive species (e.g. H
+
ions) usually
increases corrosion rate (except in passivation).

Microstructure Cold worked regions of a metal are more susceptible to corrosion
than the annealed regions.

Alloying Alloys tend to have higher corrosion rates than their pure metals (except
when passive films form stainless steels).

3.6 Passivity

With passive metals, the immunity to corrosion depends upon the properties of the
oxide film such as:
(a) thickness and impermeability to media
(b) adherence of the film to the base metal
(c) resistance of the film to chemical attack
(d) mechanical strength
(e) the ability to repair defects which may arise in the film.

Such oxide films are produced even on exposure to air, and although invisible while
in contact with the base metal, have been separated and studied. The film produced on
iron in many environments does not fulfil the above conditions, consequently
corrosion occurs. Chloride and sulphate ions are especially liable to cause film
breakdown, but chromates and phosphates promote repair.

On the other hand, aluminium and chromium form films of the impervious type and
this property is usually conferred on their alloys, so long as reducing conditions do
not prevail. Zirconium and titanium also exhibit passivity.

Passivation due to Chromium

Chromium is the chief alloying element in iron and steel for inhibiting corrosion. This
resistance is not due to the inertness of the chromium, for it combines with oxygen
with extreme rapidity, but the oxide so formed is very thin and stable, continuous and
impervious to further attack. This property is, fortunately, conferred upon its solid
solution in iron, becoming very marked as the amount exceeds 12 percent in low
carbon steels. Thus in oxidising environments, such as nitric acid, the high chromium
is initially attacked at the same rate as ordinary plain steel, but it rapidly builds up an
oxide film, known as a self-healing passive film, which efficiently protects the
underlying metal.

In the corrosion of some metals, there is a danger of break-away corrosion, which
means that after a period of a low rate of corrosion, the film of oxide becomes
discontinuous and flakes away from the surface and the corrosion rate accelerates,
e.g., zirconium in water at 400 C.


3.7 Tafel Equation

16
When there is no applied voltage, the net current density is zero. When the voltage is
increased, there is net oxidation current density. When the voltage is decreased, there
is net (reduction) current density. The relationship between the applied voltage and
the current is called Tafel Law.

Thus the rate of dissolution of a metal can be represented by an electric current.
Reaction rate per unit area of electrode current density ( i ). At equilibrium there is
no net current. Deviation of the applied potential from the equilibrium value is
responsible for driving the current. The deviation, given by E - E
0
or E - E
H
is called
overpotential or over voltage and represented by the Greek letter

= a + b log i (Tafel equation)

3.8 Exchange Current Density

For a metal M, in equilibrium with its own ions M = M
+
+ e, the rate of forward
reaction (oxidation M = M
+
+ e) is exactly balanced by the rate of the reverse reaction
(reduction M
+
+ e = M), i.e.
i
a
= i
c
= i
o

where i is the rate of reaction expressed in terms of current density and subscripts, a
and c, represent the anodic (oxidation) and cathodic (reduction) processes. i
o
is called
the exchange current. It is to be noted that exchange current is always associated with
an equilibrium condition, that is, the rate of forward (anodic) reaction equals that of
the reverse (cathodic) reaction. The net current is zero.
It has been possible to measure the exchange current density of a half reaction. The
values of exchange current density and standard electrode potential can be shown as a
point on a graph. Then the Tafel lines can be drawn beginning with this point for
M/M
+
, H
2
/2H+ etc.
3.9 Evans Diagram
When a metal is in contact with its solution, it exhibits a potential. A metal in contact
with its solution and exhibiting a potential is called a metal electrode. When the
metal and its ions are in equilibrium, the metal exhibits an equilibrium potential.
Under standard conditions, the equilibrium potential is E
0
. Under nonstandard
conditions, the equilibrium potential is E
H
and given by Nernst equation. By
equilibrium, we mean that both oxidation and reduction are taking place at equal
rates, and there is no net reaction. When the potential is changed deliberately away
from E
H
, the equilibrium is disturbed and a net reaction takes place. If the potential is
increased, there is net oxidation. If the potential is decreased, there is net reduction.
The potential of the metal may be increased by connecting it to the positive pole of a
battery or dc source or by connecting to a more noble metal. The potential of the
metal may be decreased by connecting to the negative pole of a dc source or by
connecting to a less noble metal. The increase in potential is the basis of anodic
protection (in the case of metals that can form an impervious adherent protective
oxide film layer). The decrease in potential is the basis for cathodic protection. The
increase or decrease of potential, away from equilibrium potential, is called
overpotential or polarization. When an electrode is polarized, there is a net current.
The current is a result of the polarization. Yet, usually, the polarization voltage is
17
shown on the Y axis while the current density is shown on the X axis. The graph
shows a point corresponding to standard electrode potential and the corresponding
exchange current density for an oxidation - reduction equilibrium. Beginning at this
point, one line, sloping upwards indicates oxidation. Another line, sloping downwards
indicates reduction. The excess over the standard potential is the over-potential. It is
positive for oxidation and negative for reduction.
A copper electrode exhibits a standard potential of +0.334 V and a zinc electrode
exhibits a standard potential of -0.76 V. When a copper electrode is joined to a zinc
electrode (shorted), the potential reaches an intermediate value. Then it is called a
mixed electrode. The difference between the new value and the previous value is
polarization. The oxidation of zinc is balanced by the reduction of copper, both
processes taking place at the new potential. Here the oxidation and reduction are
taking place in different metals. Zinc will continue to dissolve or corrode to the last
atom.
You have to distinguish between corrosion current and current density. Current
densities enable comparison of different corrosion rates. However, since there can be
no accumulation of charge, it is the currents involved (in oxidation and in reduction)
that are to be balanced and not the current density. That is, sum of anodic currents =
sum of cathodic currents.
A mixed electrode is an electrode or metal sample that is in contact with two or more
oxidation reduction systems. An example is zinc immersed in hydrochloric acid.
Single electrode (zinc in acid) reactions:
Zn = Zn
2+
+ 2 e
-
anodic reaction
2 H
+
+ 2 e
-
= H
2
cathodic reaction
Each has its own half-cell electrode potential and exchange current density.
The two half-cell electrode potentials cannot coexist separately on the same
electrically conductive surface (metal).
Each must polarize or change potential to a common intermediate value, the mixture
of the half-cell electrode potentials, most often called the mixed potential. The
common potential is called Corrosion potential (E
corr
) and the common current density
is called corrosion current density (i
corr
).


18



4. Types of Corrosion

4.1 Direct Chemical Attack

This form of corrosion is essentially ordinary chemical attack. The corrosive agent
such as an acid pickling solution used to clean steel surfaces, dissolves the surface
uniformly without the formation of protective layers and without selective attack of a
certain phase or component. The attack continues at an almost constant rate.

Fe + 2H
+
Fe
++
+ H
2
(pickling of steel)

This reaction differs from the indirect process of electrochemical corrosion in which
iron is dissolved as the anodic reaction and hydrogen takes part in a separate cathodic
reaction.
It is uniform chemical reaction across entire metal surface. Some areas are anodic
and some are cathodic, but these change with time giving uniform overall corrosion,
usually producing a scale or deposit. Ex. General rusting of steel, tarnishing of silver.

Direct Chemical Attack is also fundamentally electrochemical in nature. However, no
current flow is detectable, nor are there any definite anodic or cathodic areas. The
theoretical rate of a chemical attack can be affected by the formation of a protective
film on the metal surface, through secondary reactions involving the products of
corrosion, and the mechanical removal of protective films, such as by erosion, flexing
of the metal surface, or by temperature changes.

In (indirect) electrochemical corrosion, there are electric currents through parts of the
metal in which corrosion is not taking place. In direct corrosion, on the other hand,
the electrical effects involved occur in the immediate vicinity of the reaction.

4.2 Galvanic corrosion:

19
Galvanic corrosion occurs when two dissimilar metals are in electrical contact with
each other and are exposed to an electrolyte. A less noble metal, say zinc, will form
the anode and dissolve, whereas the more noble metal, say copper will act as the
cathode. Depending on the nature of the corrosive environment, the cathodic reaction
may occur either by hydrogen evolution or oxygen absorption.

Differential Couples:

From the structural point of view it is usually undesirable to connect copper and iron
together where there is going to be any moisture present. A similar generalisation
applies to carbon and iron in any sort of aqueous environment particularly a low pH
one not only from the thermodynamic stand point of the relative nobility of the
carbon but also because of the kinetic fact that most forms of carbon have low
hydrogen over-potential and therefore act as very efficient cathodes. A buried ferrous
pipe line such as a gas main, lying in any form of carbonaceous backfill, especially in
wet conditions will have a poor chance of a long life. Intergranular corrosion is
another example. Differences in concentration, oxygenation, stress or even in
temperatures will result in corrosion cell.

4.3 Differential Aeration (Concentration Cell Corrosion)

This occurs when one part of a metal is exposed to a different air concentration from
the other parts. This causes a difference in potentials between differently aerated
areas. Areas on a metal surface where the oxygen concentration is low are anodic.
Areas where the oxygen concentration is high are cathodic. Different aeration
accounts for the corrosion of metals partially immersed in a solution just below the
water line. Similarly areas on iron covered by droplets are screened from access of
oxygen and become anodic in respect to the other areas freely exposed to air. Metals
exposed to aqueous media corrode under blocks of wood or pieces of glass which
screen that portion of the metal from oxygen access. The presence of crevices as
formed by improper gasket fit can cause corrosion.

4.4 Crevice corrosion: Crevice Corrosion is the attack on the surface of a metal
partly shielded from contact with the corroding fluid, usually by non-metallic
materials. Typically, this is a concentration cell effect, the shielded area being anodic.

Concentration cells form due to differences in metal ion concentration in the
electrolyte between two regions of (same) metal piece. Metal in contact with more
concentrated electrolyte becomes Cathode; metal in contact with more dilute
solution becomes anode and corrodes. Electrons flow from the low-oxygen area on
the metal which acts as the anode to the high-oxygen area on the metal which acts as
the cathode.

To reduce crevice corrosion, use welded rather than bolted or riveted joints. Use non-
absorbing gaskets. Remove accumulated deposits. Design vessels with complete
drainage without stagnant areas.

4.5 Uniform Corrosion: Uniform unlocalized attack is the name given to the
corrosion attack which affects the whole surface of a metal simultaneously.

20
4.6 Pitting: Pitting is a localized accelerated attack resulting in the formation of
cavities or pin holes around which the metal is relatively unattacked Pitting is
usually the result of the breakdown or cracking of the protective film on a metal at
specific points. This gives rise to the formation of small anodic and large cathodic
areas. Breakdown of the protective film may be caused by mechanical factors or
certain chemicals. Stainless Steel and Aluminium show pitting in halide solutions.

Pitting corrosion is a localized form of corrosion by which cavities or "holes" are
produced in the material. Pitting is considered to be more dangerous than uniform
corrosion damage because it is more difficult to detect, predict and design against.
Corrosion products often cover the pits. A small, narrow pit with minimal overall
metal loss can lead to the failure of an entire engineering system. Pitting corrosion,
which, for example, is almost a common denominator of all types of localized
corrosion attack, may assume different shapes.

Pitting is initiated by:

a. Localized chemical or mechanical damage to the protective oxide film; water
chemistry factors which can cause breakdown of a passive film are acidity,
low dissolved oxygen concentrations (which tend to render a protective oxide
film less stable) and high concentrations of chloride (as in seawater)

b. Localized damage to, or poor application of, a protective coating

c. The presence of non-uniformitys in the metal structure of the component,
e.g. nonmetallic inclusions.

Pitting corrosion can produce pits with their mouth open (uncovered) or covered with
a semi-permeable membrane of corrosion products. Pits can be either hemispherical
or cup-shaped.

Apart from the localized loss of thickness, corrosion pits can also be harmful by
acting as stress raisers. Fatigue and stress corrosion cracking may initiate at the base
of corrosion pits.

4.7 Intergranular Corrosion Precipitation of certain compounds at grain boundaries
leaves the solid solution adjacent to the grain boundary impoverished in one
constituent. The depleted zone is anodic with respect to the precipitated compound,
as well as center of the grain, so that it will be preferentially attacked by the corrosive
environment (CuAl
2
ppt in Al-Cu alloys, weld decay in austenitic stainless steel).

4.8 Erosion Corrosion: Erosion-corrosion is the attack caused by the combined
effect of corrosion and wear produced by the turbulent flow of gases, vapours and
liquids, and also by the rubbing action of solids over a metal surface. Erosive action
removes the protective films. It is frequently encountered in condenser tubes, piping,
agitators, or vessels in which streams of liquids or gasses emerge from an opening and
strike the side wall.

Erosion Corrosion, as the name implies, occurs when the corrosion products which
would normally afford a protective film are scoured off by moving fluids, particularly
21
if the fluids contain abrasive materials. The erosion will expose clean metal, and
develop a physical pattern so obviously a result of erosion that the corrosive factor
may not be recognized.

Cavitation or Impingement Attack is a process which is very similar to erosion. In
cavitation, collapsing gas bubbles in regions of turbulence and local pressure
fluctuations may activate serious corrosion. Condenser tubes and pump impellers are
subject to this type of attack.

4.9 Stress Corrosion: Stress corrosion or stress corrosion cracking is a term
describing the combined effect of static tensile stresses and the corrosive environment
or a metal. The stresses can be either residual or applied. The residual stresses may
result from unequal cooling, from precipitation and phase transformation, from poor
design, or from cold working and welding. Stress corrosion is characterised by a
highly localised attack occurring when over-all or uniform corrosion is very low.

Season cracking is a term applied to stress corrosion of copper alloys, mainly brasses,
which when highly stressed under go cracking in atmosphere containing traces of
ammonia.

Stainless steels may show cracking on acid chloride solutions, sea water and H
2
S.

Stress Corrosion Cracking results when even a very small pit forms in a metal under
stress. The concentrated stress may either deepen and extend the pit, or crack any
protective film which might tend to form. Under continued exposure to the corrosive
medium and stress, the crack extends by alternate corrosion and stress failure.

4.10 Corrosion Fatigue Corrosion fatigue may be described as the reduction of
fatigue strength by corrosive environment. In a corrosive environment the corrosion
fatigue strength is much below the fatigue limit. The damage ratio (i.e corrosion
fatigue strength divided by air fatigue strength) due, for example, to a salt water
environment is about 0.4 for Aluminium alloys, 0.5 for Stainless Steels, 0.2 for plain
carbon steels and 1.0 for Cu.

Corrosion Fatigue occurs when a metal is subjected to alternating stress and relief in a
corrosive environment. Metal failure occurs much more rapidly under the alternating
stress than under either stress or relief alone. Continuous removal of protective films,
and the repeated exposures of clean metal by small stress failures cause corrosion
fatigue.

4.11 Hydrogen Embrittlement and hydrogen attack results when atomic hydrogen,
contained in chemical and refinery processes or produced electrolytically by the
process, penetrates onto the grain boundaries of steel producing micro cracks,
blistering and loss of ductility. The atomic hydrogen combines into molecules, cannot
escape, resulting in blistering and laminations.

4.12 Caustic Embrittlement is usually the result of steam escaping through a
crevice, such as between boiler plates or pipe flanges. The escaping water, usually in
22
a fissure of steam, becomes highly concentrated, and the increased alkalinity of the
concentrated water causes failure by stress corrosion.

Caustic embrittlement is a stress corrosion phenomenon occurring on mild steel
exposed to alkaline solutions at high temperatures and stresses. In steam boilers,
water of high alkalinity attacks the steel plate at the crevices near rivets.

4.13 Dry Oxidation and Tarnish result when the clean surfaces of metals are
exposed to air or other gasses to form oxides or other compounds on the surface of the
metals. Many of these films are invisible at room temperature, but at higher
temperatures these films may reach considerable thickness. The rate of film growth is
usually greater at higher temperatures. At higher temperatures, and more particularly
under changes of temperature, the film may crack or spall to expose fresh metal to
attack. Bending or stressing the metal can induce or increase the spalling. The
presence of sulfur-bearing gasses may greatly increase the rate of attack. And the
presence of moisture will accelerate attack, and complicate it by permitting
electrolytic corrosion.

4.14 Dezincification One constituent of an alloy, such as the zinc in brass or bronze,
may be selectively removed, leaving a porous replica of the original part. Often the
whole alloy is initially dissolved, with one element redeposited in spongy form.

4.15 Graphitization is most often seen as the electrolytic corrosion of cast iron, and
often takes a form very similar to the dezincification of brass. Iron is removed
selectively, leaving a replica composed of carbon or graphite.

4.16 Fretting Corrosion. Metal surfaces in close physical contact, in a corrosive
environment, and subjected to vibration, can accelerate corrosion attack by the
continuous removal of protective films. Machine parts with small relative motion and
high unit loads are subject to fretting corrosion.