Corrosion Science & ENGINEERING

Supplement to CH111 course

Part II

KG SREEJALEKSHMI

Department of Chemistry

Indian Institute of Space Science and Technology

Thiruvananthapuram
DEFINITION

According to Ulick R. Evans, the British scientist who is considered the "Father of Corrosion
Science", "Corrosion is largely an electrochemical phenomenon, which may be defined as
destruction of a material by chemical or electrochemical agencies."

Corrosion is the degradation or deterioration of a material, usually a metal, by chemical or

electrochemical reaction with its environment. Or simply, Corrosion is extractive metallurgy
in reverse.

CAUSE OF CORROSION

Most of the metals (except noble metals Au & Pt) exist in nature in combined forms like
chlorides, silicates, oxides, carbonates etc. When these metals are separated from their ores to
get them in the pure form, they show a natural tendency to revert back to their combined forms.
During this process, they usually combine with atmospheric oxygen to form oxides or
depending upon the nature of the environment sulphides, carbonates etc may also be formed.
This process of reverting back to the combined state usually shown by a metal is termed
corrosion of the metal (weeping of metals). Such a process will result in a change in the
properties of the metal which will limit its applications.

In general terms corrosion is the chemical or electrochemical reaction between a material,

usually a metal, and its environment that produces a deterioration of the material and its
properties. The environment could be of any type such as atmosphere, water, acids, alkalies,
gases, soil etc and the interaction leading to corrosion can take place at any temperature. The
term corrosion may also be applied to weathering of timbers and concrete, leaching of glass,
cracking of plastics etc. In the modern world where miniaturization of devices and equipments
are so important, corrosion in even a very small scale may cause the damage or limit the utility
of the whole device.

Examples of corrosion

1. Rusting of iron (Fe3O4 formation due to reaction of iron with moisture and air)
2. Formation of basic copper carbonate [CuCO3 + Cu(OH)2] on the surface of Cu as a
green film when exposed to moist air containing CO2.

In nature, all spontaneous changes occur with a release of free energy from the
system to the surroundings at constant temperature and pressure.

Corrosion is a spontaneous process where free energy is released and in the process metals
return to their stable state.

The driving force for corrosion reaction is the chemical energy - energy stored in chemical
bonds of substances – internal energy. To explain the corrosion phenomenon, we often use
transition state theory which considers that for

A+ B = (AB)* = C + D
the transition sate must be of higher free energy than the sum of the free energies of the
separate species.

For corrosion reaction, the rate constant can be shown to be related to the size of the free
energy barrier according to the equation

kcorr = A exp(G‡/RT)

where A and R are constants, and T is the absolute temperature. From the equation, as T
increases the rate constant (and hence the rate) also increases. But when the size of the barrier
(G‡) is increased, the rate constant decreases.

If we consider the reverse process, it cannot be spontaneous, because there is an increase in

free energy upon conversion of C and D into A and B. Furthermore, there is a bigger free
energy barrier for the new reactants, C and D, to cross. The Transition State Theory says that
the reverse process is possible, but occurs at a much reduced rate, represented by an equation
similar to the above equation in which the activation free energy has been increased from G‡
to ( G + G‡ ). The reverse process is possible only on the molecular scale where the energies
of an individual C and D pair may be such as to allow the formation of the transition state.
(Remember that our rule applies to an overall free energy change for a bulk system.) The
reverse process occurs at a rate far less than the rate of the forward process, so the net reaction
observed on the large scale will always appear to be a steady conversion of A + B into C + D.
For the reverse process to occur in the bulk system, energy must be supplied to the system
(eg. as in electrolysis).

Points to remember:

Nature is always concerned with minimizing energy. Corrosion is a natural occurring

process, predicted by thermodynamics laws.

high energy states (metal) = low energy states (metals compounds)

It is this tendency of metals to recombine with elements presents in the environments that
leads to the phenomenon known as Corrosion. The low energy corrosion product is not the
same as an ore (may be similar), the energies of the ore and the corrosion product may well
be comparable.

Tendency to corrode and rate of corrosion

Tendency to corrode is determined by the free energy difference G between a metal and its
corrosion product. Rate of corrosion is determined by the size of the energy barrier (the free
energy of activation)

Rate of corrosion reaction = kcorr [reactants]

kcorr =A exp (-G*/RT); A= constant; R= gas constant, T= absolute temperature

G* is the minimum amount of energy required to drive the molecules/atoms over the
activation energy barrier, so that appreciable reaction can take place.
Free energy is the single factor to determine the possibility of a corrosion reaction.

Why do gold, platinum and other precious metals not corrode ?

 the energetics may not be favorable

 the size of activation energy barrier may be too great (the rate is extremely slow)

Now you understand the driving force for corrosion to occur. It is also very important to have
a fairly good idea about the consequences of corrosion. The following paragraphs will provide
you with most important consequences of corrosion which will help you to understand the
significance of studying corrosion science and corrosion control.

CONSEQUENCES OF CORROSION

Consequences of corrosion can be discussed under various sub-headings among which

economic, health, safety, technological, and cultural consequences are more serious to our
society.

ECONOMIC ASPECTS OF CORROSION

It is estimated that hundreds of thousands crores is lost every year due to corrosion!

Although corrosion is a slow process occurring mainly at the surfaces of metals, enormous
losses occur each year in all the countries around the world. These losses are classified into
Direct and Indirect losses.

Direct loss – include price of the corroded metal and the cost of replacement including labor.

Indirect loss – loss of efficiency, shut down loses in the form of lost production, loss of product
due to leakage, wastage of metal due to overdesign and cost involved in the prevention of
corrosion.

Loses due to corrosion varies from country to country, depending upon the climatic conditions.
In India problems due to corrosion are more serious than those in cold countries due to the
tropical climate. According to a rough annual estimate, direct loss due to corrosion is estimated
to be between Rs 250-260 crores and the money spent on its prevention is about 45-60 crores.
Thus it is very important to understand the mechanism of corrosion so that it can be predicted
and minimized whereby the money loss can be reduced.
In India, the direct loss due to corrosion amounts to Rs. 200 crores/annum and the money spent
for controlling corrosion is nearly 50 crores.

Fortunately, most useful metals react with the environment to form more or less protective
films of corrosion reaction products that prevent the metals from going into solution as ions.

HEALTH AND SAFETY ASPECTS

With the advancement of biomedical technology, there is an increase in the use of metal
prosthetic devices in the body, such as pins, rods, plates, hip joints, pacemakers, and other
implants. Even though new alloys and better techniques of implantation have been developed,
corrosion continues to create problems. Examples include failures through broken connections
in pacemakers, inflammation caused by corrosion products in the tissue around implants, and
fracture of weight-bearing prosthetic devices.

Another significant problem related to safety is corrosion of structures, which can result in
severe injuries or even loss of life. Safety is compromised by corrosion contributing to failures
of bridges, aircraft, automobiles, gas pipelines etc. – the whole complex of metal structures and
devices that make up the modern world.

TECHNOLOGICAL ASPECTS

The development of new technology requires new materials which are required to withstand,
in many cases simultaneously, higher temperatures, higher pressures, and more highly
corrosive environments. Corrosion problems that are less difficult to solve affect solar energy
systems, which require alloys to withstand hot circulating heat transfer fluids for long periods
of time, and geothermal systems, which require materials to withstand highly concentrated
solutions of corrosive salts at high temperatures and pressures. Another example, the drilling
for oil in the sea and on land, involves overcoming such corrosion problems as sulfide stress
corrosion, microbiological corrosion, and the vast array of difficulties involved in working in
the highly corrosive marine environment. In many of these cases, corrosion is a limiting factor
preventing the development of economically or even technologically workable systems.

CULTURAL ASPECTS

The highly polluted environments that are now prevalent in most of the countries of the world
initiate corrosive processes which will accelerate the deterioration of precious artifacts inside
the world's museums.

To explain the corrosion phenomenon observed in the nature, the different corrosion
processes are classified on the basis of the mechanisms through which they propagate. Often
we explain the real corrosion problems with the help of one or more of these mechanisms.

CLASSIFICATION OF CORROSION

CORROSION

DRY CORROSION WET CORROSION CONCENTRATION CELL

(CHEMICAL) (ELECTROCHEMICAL) CORROSION
DRY CORROSION

Occurs through direct chemical action of environment/atmospheric gases (O2, halogen, SO2, H2S, N2
or anhydrous inorganic liquid) with metal surfaces in immediate proximity.

OXIDATION CORROSION CORROSION BY OTHER GASES LIQUID METAL

CORROSION
(other than O2)

a. Oxidation Corrosion

Occurs due to direct action of O2 at high or low temp., usually in the absence of moisture.
Highly reactive metals (alkali & alkaline earth) are oxidized even at low temp. (Li, Na, K, Rb,
Be, Ca, Sr etc). At high temp. all metals except Ag, Au & Pt are oxidized.

Reactions
M Mn+ + n ē (formation of metal ion, oxidation)

n/2 O2 + n ē n O2 -

In the first step, there is adsorption of oxygen on to the metal surface which results in the
formation of an oxide layer on the metal surface. Further diffusion (metal out or O2- in) as in
the figure below is governed mostly by the nature of the oxide layer

To explain the corrosion due to oxidation we need to understand the different types of oxides
commonly encountered in corrosion scenes.
They are
1. Stable oxide layer
2. Unstable oxide layer
3. Volatile oxide layer
4. Porous oxide layer
 The stable oxide layer is characterized by fine-grained particles which tightly adhere
forming an impervious layer over the metal surface. Hence it acts as a protective layer.
Al2O3 is an example for a stable oxide layer.

The unstable oxide layer is one whose formation is reversible. For such metals, oxidation
corrosion is not possible. Inert metals like Pt are classified under this category.

The volatile oxide layer is one which is volatilized soon after the formation. This will
result in the exposure of more and more metal surface to the corroding environment. It is a
continuous process posing a very dangerous situation where the whole of the metal gets
damaged. MoO3 and WO3 are examples of volatile oxides.

In the porous oxide layer category, the oxide formed will have cracks through which
oxygen can go in. After some time the whole metal may get damaged. Fe and Cr oxides are
porous in nature.

By observing the nature of the oxide formed, it is often possible to predict the corrosion
tendency of a metal. This is done by applying Pilling-Bedworth Rule.

Rule to determine the protective (non-porous) or non-protective (porous) nature of

the oxide film
The PB rule states that
• If the volume of the oxide layer is greater than or at least equal to the volume of
the metal from which it is formed, the oxide layer is protective and hence non-
porous

• If the volume of the oxide layer is less than the volume of the metal from which it
is formed, the oxide layer is porous and hence non-protective
The PB ratio R is given by

Volume of metal oxide formed Md

R= =
Volume of metal consumed Dam
where M and D are the mass and density of the metal oxide respectively and m and d
are the mass and density of the metal respectively. Here ‘a’ is the number of metal
atoms (stoichiometry) that go into the formation of one molecule of the oxide.
Eg; a is 1 for CuO, 2 for Cu2O, 3 for Fe3O4 etc.

Pilling-Bedworth ratio, R, for an oxide indicates its potential as a thin film

material
(a) For, R<1, the film tends to be porous if it experiences volume shrinkage during film
growth

(b) For 1<R<2, it has a much better coverage

(c) For R>2, large volume expansion accompanies oxide growth, and cracks can develop
due to large compressive stress
 The following table gives the PB ratios for some oxides

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson

(a) Mg - porous oxide film

Learning™ is a trademark used herein under license.

(b) Al - protective, adherent,

nonporous oxide film

(c) Fe – layer that spills off

the
surface and provides
poor protection

You can find the PB ratios for given metal oxide mathematically and explain the
nature of the film formed.

Problem

The density of aluminum is 2.7 g/cm3 and that of Al2O3 is about 4 g/cm3. Molecular
weight of Al2O3 is 101.96 and that of aluminum is 26.981. Describe the characteristics
of the aluminum-oxide layer formed.
Solution
Required equation for the formation of the oxide is 2Al + 3/2O2  Al2O3
Substitute the values in the equation for R and you will find that the value is 1.28.
This oxide layer is non-porous and hence protective as observed experimentally.

In some case the thermodynamics will predict the formation of stable oxides, but the
protective nature of the oxide film can be predicted by applying PB rule only. For
example consider the case of MgO. The free energy of formation of MgO is predicting
a stable oxide layer. But if you look at the PB ratio, you will see that the MgO oxide is
porous and hence non-protective.
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc.
Thomson Learning™ is a trademark used herein under license.

b. Corrosion by other gases (other than O2)

In the presence of dry atmosphere gases like SO2, H2S, Cl2, NOx can induce corrosion
of metallic components which are classified under dry corrosion. The corrosion
products of the reaction of these gases with metal may be protective or non-protective.
Egs: Dry Cl2 reacts with Ag and forms AgCl which is a protective layer, while with
Sn the product is SnCl4 which is volatile.
In petroleum industries at high temperatures, H2S attacks steel forming FeS scale
which is porous and interferes with normal operations.

c. Liquid Metal Corrosion

This is a major corrosion problem encountered due to flowing liquid metals and is also
called liquid metal embrittlement. In several industries, molten metal passes through
metallic pipes and causes corrosion due to dissolution or due to internal penetration.
For example, liquid metal mercury dissolves most metals by forming amalgams,
thereby corroding them. Another example is the corrosion possible in fast breeder
reactors which use liquid sodium as the coolant.
In the classic example of liquid copper metal embrittlement of steel, Cu penetrates
along the austenite grain boundaries when the carbon steel is at a temperature of 1100
°C.

(more information can be found at http://dx.doi.org/10.1590/S1516-14392004000100015)