Corrosion

Wide variety of metals/alloys used in daily

equipments/machineries/industrial structures/bridges etc have
a natural tendency to get deteriorated by the environment
(air/water/soil/temperature) to which it is exposed.

WHY DO METALS CORRODE ?

Naturally metals exist in the form of compounds (ores) and are
in thermodynamically stable (lowest energy state).

Extracted metals from these compounds are in high energy

state (large amount of energy is spent in converting a
compound into pure metallic form).

When a metal is exposed to environment has a tendency to get

converted to their stable and lowest energy state.
 Corrosion is the destruction/deterioration of metals by the
surrounding environment through chemical or electrochemical
changes resulting in the formation of compounds.

It is an oxidation process. It results in the loss of metal.

Examples: Formation of rust on the surface of iron,

formation of green film on the surface of copper.

The responsible factors for the corrosion of a metal are the

metal itself, the environmental chemicals, temperature and the
design.
Metallic corrosion reactions are electrochemical in nature.
electrochemical reaction is associated with charge transfer in addition
to mass transfer.
All electrochemical reactions may be split into two or more partial
oxidation and reduction reactions.

ELECTROCHEMICAL CELL
Every electrochemical corrosion cell must have
four components
1. The anode, which is the metal that is corroding

2. The cathode, which is a metal or other electronic conductor

whose surface provides sites for the environment to react

3. The electrolyte (the aqueous environment), in contact with both

the anode and the cathode to provide a path for ionic conduction

4. The electrical connection between the anode and the cathode to

allow electrons to flow through them.
 ANODE REACTIONS
Anode metal corrodes and metal ions get into solution as:
M  Mn+ + ne-
If steel is corroding,
Fe  Fe2+ + 2e-
If Aluminum is corroding,
Al  Al3+ + ne-
These reactions are also called Oxidation reactions.

CATHODE REACTIONS
The cathodic reaction consumes the electrons generated by the
anodic reaction.

In dissolved oxygen present in the neutral/alkaline medium

reacts with electrons and water molecule to generate hydroxide
ion
O2 + 2H2O + 4e-  4OH-
 OTHER CATHODE REACTIONS

Hydrogen ion reduction or hydrogen evolution:

2H+ + 2e-  H2

Oxygen reduction in acid solutions:

O2 + 4H+ + 4e-  2H2O

Metal ion reduction:

Mn+ + e-  M+(n-1)

Metal deposition:
Mn+ + ne-  M
 TYPES OF CORROSION
The process of corrosion of metals depends on the environment to
which it is exposed
DRY CORROSION/CHEMICAL CORROSION/DIRECT CHEMICAL ATTACK
If metal is exposed to dry environment (gases such as
oxygen/chlorine/sulphur dioxide/hydrogen sulphide)  formation its
respective compounds: CHEMICAL CORROSION

DRY CORROSION CAN OCCUR DUE TO

a) Oxidation corrosion
b) Corrosion of gases
c) Liquid metal corrosion

OXIDATION CORROSION
Metals are attacked by dry oxygen (in absence of moisture) at low/high
temperature- oxidation type of corrosion.
Alkali/alkaline earth metals undergo oxidation at low temperatures
Metals like Fe/Al etc (except noble metals) are oxidised at high
temperatures.
MECHANISM
Oxidation starts at the exposed surface of metal.
The metal loses electrons and changes to metal ions, whereas oxygen
accepts the electrons and changes to oxide ion.

EXAMPLES
Mg  Mg2+ + 2e- (oxidation) Al  Al3+ + 3e- (oxidation)
0.5O2 + 2e-  O2- (reduction) 0.5O2 + 2e-  O2- ] × 3 (reduction
Mg + 0.5O2  MgO Al + 1.5O2  Al2O3
During oxidation of a metal, thin film of metal oxide (stable) formed on
the metallic surface protects the metal from further corrosion.
Thus, the nature of metal oxide formed on the surface of a metal plays
an important role in the process of corrosion.
Oxides of Pb/Al/Sn are stable and hence inhibit further corrosion. They
form a stable, tightly adhering oxide film.
If oxygen diffusion across the thin layer, further corrosion is possible.
In case of porous oxide film (unstable oxide), atmospheric gases pass
through the pores and react with the metal and the process of
corrosion continues to occur till the entire metal is converted into
oxide.
Porous oxide layer is formed by alkali/alkaline earth metals.

Molybdenum forms a volatile oxide film of MoO3 which accelerates

corrosion.
Au, Ag, Pt form unstable oxide layer which decomposes soon after the
formation, thereby preventing further corrosion.
 PILLING-BEDWORTH RULE

This rule is helpful in deciding whether the oxide film formed on the metal
surface is porous or non-porous.

According to this rule,

Specific volume ratio : Volume of metal oxide/volume of metal

PB < 1 : then it will be porous for diffusion of Mn+ and O2- and oxidation
will take place (brittle coating-cracks are developed).

PB > 1 : then the oxide film will be non-porous (uniformly cover metal):
surface and is protective
PB >> 1 : brittle coating-cracks are developed
Pilling-Bedworth ratio for some oxides
K2O Na2O MgO Al2O3 NiO Cu2O Cr2O3 Fe2O3
0.41 0.58 0.79 1.38 1.60 1.71 2.03 2.16
 (ii) CORROSION BY OTHER GASES (Cl2, F2, SO2, H2S, NOx)

In dry atmosphere (absence of oxygen), these gases react with metal

and form corrosion products which may be protective or non-protective.
Dry Cl2 reacts with Ag to form AgCl which is a protective layer,
while Sn reacts to form SnCl4 (non protective) is volatile.
At high temperatures, H2S reacts with iron to form FeS which is porous
and interferes with normal operations.
(III) LIQUID - METAL CORROSION
Molten metal/liquid passes through metallic pipes/solid metal surface
causes corrosion.
It weakens the solid metal due to
(i) penetration of the liquid metal,
(ii) dissolution of the solid metal in liquid metal.

For example:
corrosion of cadmium rods taking place due to sodium metal acting as
coolant in nuclear reactors.
3) WET/ELECTROCHEMICAL/IMMERSED CORROSION

It is a common type of corrosion of metal in aqueous corrosive

environment.

This type of corrosion occurs

i) when the metal comes in contact with a conducting liquid
ii) when two dissimilar metals are immersed or dipped partly in a
solution.

According to this theory, there is the formation of a galvanic cell on

the surface of metals.

Some parts of the metal surface act as anode and rest act as
cathode.

The chemical in the environment and humidity acts as an electrolyte.

Oxidation of anodic part takes place and it results in corrosion at

anode, while reduction takes place at cathode.

The corrosion product is formed on the surface of the metal between

anode and cathode.
 3) WET/ELECTROCHEMICAL/IMMERSED CORROSION

EVOLUTION OF HYDROGEN
The process of corrosion in which H2 is liberated is called evolution of
hydrogen type corrosion.
The hydrogen evolution type of corrosion occurs in acidic medium.
The process of dissolution of iron as Fe2+ occurs at the anodic areas of
the metal resulting in the liberation of electrons
Fe  Fe2+ + 2e- (oxidation)

The liberated electrons flow from the anodic to the cathodic area of
the same metal and give rise to the corrosion current.
The electrons liberated will reduce H+ ions at the cathodic area.
2H+ + 2e-  H2
 3) WET/ELECTROCHEMICAL/IMMERSED CORROSION
ABSORPTION OF OXYGEN
Rusting of iron
At anodic area of the metal, iron dissolves as Fe2+ ions with liberation
of electrons (anode gets corroded):
Fe  Fe2+ + 2e- (oxidation)

The liberated electrons flow from the anodic to the cathodic area,
where it reduces the oxygen absorbed to form OH- ions
0.5O2 + H2O + 2e-  2OH-
Fe(OH)2 is precipitated on the surface of the metal due to diffusion of
both Fe2+ and OH-
Fe2+ + 2OH-  Fe(OH)2 
If the Fe(OH)2 is exposed to oxygen in the environment, it gets
converted to Fe(OH)3/Fe2O33H2O
 Differences between dry and wet corrosion
DRY CORROSION WET CORROSION
Corrosion occurs in the absence of Corrosion occurs in presence of
moisture conducting medium.
It involves direct attack of chemicals It involves formation of
on the metal surface electrochemical cells.
The process is slow. It is a rapid process.
Corrosion products are produced at Corrosion occurs at anode but rust is
the site of corrosion. deposited at cathode.
The process of corrosion is uniform. It depends on the size of the anodic
part of metal.
 Differences between chemical and electrochemical corrosion
CHEMICAL CORROSION ELECTROCHEMICAL CORROSION
It occurs in dry condition. It occurs in wet condition in the
presence of moisture and electrolyte.
It involves the chemical attack of It involves electrochemical attack of
oxygen or other gases corrosive environment on the surface
of the metal.
It can occur at homogeneous as well It occurs only on heterogenous metal
as heterogenous metal surfaces. surfaces.
It is uniform in nature throughout the It is not uniform.
surface of the metal.
It is a slow process taking place by It is a fast electrochemical process. It
chemical reaction of atmospheric proceeds through the cells.
gases.
Corrosion products accumulate at the Corrosion products accumulate
place where corrosion occurs i.e., at somewhere between the area of
the anode. anode and cathode.
Its mechanism is explained on the Its mechanism is explained on the
basis of absorption. basis of electrochemical reactions.
 TYPES OF CORROSION

There are basically eight types of corrosion

Uniform corrosion

Pitting corrosion

Transgranular and Intergranular (Intercrystalline) corrosion

Exfoliation corrosion

Stress corrosion

Crevice corrosion

Galvanic corrosion

Erosion
GALVANIC CORROSION
When two dissimilar metals are in direct contact in a conducting liquid,
one of the two may corrode. This is called galvanic corrosion.
The other metal will not corrode; it may even be protected in this way.
Unlike other types of structural corrosion, galvanic corrosion does not
depend on the metal’s texture, temper, etc.
Galvanic corrosion may occur with any metal, as soon as two are in
contact in a conductive liquid.
It works like a battery.
The appearance of galvanic corrosion is very characteristic and highly
localized in contact zone with the other metal.
The zone affected by galvanic corrosion often has a shinier aspect than
the rest of the surface.
 Galvanic corrosion e.g., Zn and Cu, Zn and Ag, Fe and Cu.
Zinc with higher oxidation potential than copper acts as anode and the
electrons flow from anodic metal (Zn) to cathodic metal (Cu). The anodic
metal is corroded, while cathodic metal remains protected.
In acidic solution, the corrosion occurs by the evolution of hydrogen
Zn2+ + 2H+  Zn2+ + H2

In neutral or slightly alkaline medium, oxygen absorption takes place.

H2O + 0.5O2 +2e-  2OH-
 Galvanic corrosion can be minimized by

(i) avoiding galvanic couples i.e., minimising the potential

difference between the concerned metals
(ii) providing an insulating material between the two metals
(iii)avoiding the suitable medium for corrosion
(iv)By polishing the metals

These combinations should be avoided.

(i) Greater the potential difference between the two metals

forming the galvanic cell, greater is the corrosion.
(ii) A suitable medium is required for the flow of electrons.
(iii) Exposed surface area of the metal
Differential aeration corrosion or Concentration cell corrosion
when the metal surface is exposed to an
electrolyte of varying concentration or of
varying aeration.

It also occurs when one part of the metal is

exposed to a different air concentration from
the other part.

It has been observed that poorly oxygenated

parts become anodic and are corroded, whereas
more oxygenated portion acts as cathode.

It occurs when a metallic surface is partially immersed in a solution and

partially exposed to the atmosphere.

Zn is partially immersed in a dilute solution of NaCI and solution

 UNIFORM CORROSION
This type of corrosion develops as pits of very small diameter, in the
order of a micrometer, and results in a uniform and continuous
decrease in thickness over the entire surface area of the metal.
The rate of uniform corrosion can be easily determined by measuring
the mass loss/the quantity of released hydrogen.
Example:
Steel or zinc in dilute H2SO4
Uniform attack can be prevented or reduced by
Proper materials including coatings
Inhibitors
Cathodic Protection
 PITTING CORROSION
This localized form of corrosion is characterized by the formation of
irregularly shaped cavities on the surface of the metal.

There is a stagnant solution at the bottom of the pit i.e a lower oxygen
concentration is outside of the pit than inside resulting in the another
oxygen concentration cell.
Corrosion takes place at the bottom of the pit than inside.

As the pit gets deeper, the solution at the bottom of the pit becomes
more stagnant creating more driving force to promote corrosion.
A pit is self catalysing in nature.
 II. PITTING CORROSION
A small part of the metal surface covered by an impurity/water has a
low oxygen concentration and it acts as an ANODE,
uncovered metal surface acts as a CATHODE due to high oxygen
concentration.
The small covered area acting as ANODE gets corroded giving rise to
localized spots (pits), pinholes and cavities in the metal. Once a small
pit is formed, the rate of corrosion increases.

It is a localized corrosion and accelerated corrosion takes place at the

anodic region causing minute pits/pin holes on the surface of the
metal.
It can also be explained based on differential areation corrosion.
Unlike uniform corrosion, the intensity and rate of pitting corrosion
cannot be assessed neither by determining the mass loss nor by
measuring released hydrogen.
PITTING CORROSION CAN BE ASSESSED USING THREE CRITERIA :

the density, i.e. the number of pits per unit area,

the rate of deepening and the probability of pitting.

In fact, these measurements do not make sense because a very deep

and isolated pit results only in a small mass loss, where as a very large
number of superficial pits can lead to a larger mass loss.
 PITTING CORROSION
EXAMPLE
The anodic areas of the metal (M = Zn/Fe) gets corroded in a corrosive
environment due to oxidation process, liberating electrons.
Zn  Zn2+ + 2e-
Fe  Fe2+ + 2e-
Potential occurs due to the formation of anodic and cathodic areas of
the metal surface, which causes the flow of corrosion current between
the two differentially aerated areas of the metal.

The more oxygenated area of the metal (Zn/Fe) is protected and o2

absorption occurs at the cathode region. The reduction reaction is
0.5O2 + H2O + 2e-  2OH-

Zinc produces a corrosion product Zn(OH)2

When iron is exposed to an environment rich in oxygen, Fe(OH)2
formed gradually oxidised to Fe(OH)3.

The net corrosion reaction due to rusting of iron, thus

4Fe + 3O2 +6H2O  2(Fe2O33H2O) (rust)
TRANSGRANULAR AND INTERGRANULAR (INTERCRYSTALLINE )
CORROSION

Within the metal, at the level of the grain, corrosion may propagate in
two different ways :
(i) It spreads in all directions,
(ii) corrosion indifferently affects all the metallurgical constituents;
there is no selective corrosion.
(iii) This is called transgranular or transcrystalline corrosion because it
propagates within the grains.
Intergranular corrosion
An attack on the grain boundaries of a metal.
A highly magnified cross-section of any commercial alloy shows the
granular structure of the metal.
It consists of quantities of individual grains and each of these tiny
grains have a clearly defined boundary which chemically differs from
the metal within the grain.
The grain boundary and the grain center can react with each other as
anode and cathode when in contact with the electrolyte.
(ii) IT FOLLOWS PREFERENTIAL PATHS:

corrosion propagates at grain boundaries.

Unlike transgranular corrosion, these forms of intercrystalline

corrosion consumes only a very small amount of metal, hence mass
loss is not a significant parameter for assessment of this type of
corrosion.

It is not detectable which naked eye but requires microscopic

observation, typically at a magnification of 50.

When penetrating into the bulk of the metal, intercrystalline corrosion

may lead to a reduction of mechanical properties and even lead to the
rupture of components.
 CORROSION
EXFOLIATION

Exfoliation corrosion is a type of selective corrosion that propagates

along a large number of planes running parallel to the direction of
rolling or extrusion.

The attack has a rather laminated appearance and whole layers of

material are corroded.

The attack is usually recognized as blistered/flaky surface.

Between these planes are very thin sheets of metal that are not
attacked, but gradually pushed away by the swelling of corrosion
products, hence the term exfoliation corrosion.

The metal will swell, which results in the this form of corrosion.

In aluminium alloys: we observe this type of corrosion.

STRESS CORROSION

This type of corrosion results from the combine action of a mechanical

stress (bending, tension) and a corrosive environment.

When any portion of a metal is under stress, highly localised corrosion

takes place in a “Specific corrosive environment”.
In stress corrosion, the corrosive agents are highly specific and
selective.

Each of these parameters alone would not have such a significant

effect on the resistance of the metal or would have no effect at all.
 STRESS CORROSION

EXAMPLE

KOH/NaOH solution environment attacks stressed mild steel.

Stressed portion of brass corrodes in the presence of ammonical
environment.

The stress corrosion of metals can also be explained on the basis for
electrochemical theory.

In a corrosive environment, the stressed portion of the metal acts as

the anodic areas with respect to the unstressed (cathodic) area and
undergoes corrosion.

A metal sheet is shown in figure has a stress at the bend region.

The presence of such stress on metal results in strain, causes a

‘localised area of higher electrode potential’.

This strained localised zone, thus becomes chemically reactive and

sensitive to even mild corrosive environment.
 STRESS CORROSION

The bend region is vulnerable for corrosion, while the unrestricted

(cathodic) region of the metal is protected from corrosion.

The types of stress corrosion are

i) Season cracking
ii) Caustic cracking
iii) Hydrogen embrittlement
iv) Stress corrosion cracking

SEASON CRACKING
Pure copper is less prone to stress corrosion.
The presence of impurities can result in a sensitivity for corrosion.
The stressed grain boundaries in brass get corroded in mild ammonia
solution and induces season cracking.

This strained localised zone, thus becomes chemically reactive and

sensitive to even mild corrosive environment.
 STRESS CORROSION
CAUSTIC EMBRITTLEMENT
Occurs at the stress areas such as crevices or rivets, joints/bend portion
of steam boilers/heat transfer equipments at high pressure in which
alkaline water attacks the mild steel.
The water of the steam boiler is softened by the addition of sodium
carbonate, which makes water alkaline due to the action of sodium
carbonate at high pressure
Na2CO3 + H2O  2NaOH + CO2 
The NaOH formed moves into the crevices of rivets/cracks by capillary
action. Due to the evaporation of water in boilers, the concentration of
NaOH in these cracks and crevices increases.
This corrosive environment attacks the mild steel and as a result, sodium
ferrate (Na2FeO2) is formed, which decomposes from the point of its
formation.
Na2FeO2 + 4H2O  6NaOH + Fe3O4 + H2
Regenerated NaOH enhances corrosion attack and mild steel and Fe3O4 is
deposited as a rust.
This type of stressed corrosion is dangerous because it leads to boiler
failure.
 STRESS CORROSION
HYDROGEN EMBRITTLEMENT CORROSION

Caused a ductile material to fail without localised yielding or shearing.

This damage takes place at cathode, an area that we normally think is

safe (since corrosion has to take place at the anode).

Hydrogen ions are reduced to hydrogen molecules at the cathode.

Those atoms usually pair up to become hydrogen molecules.

These molecules harmlessly bubble off as hydrogen

gas.

However, some metals are very susceptible to

letting hydrogen atoms permeate into the grains.

This is done while the hydrogen exists as a atom,

before it becomes a molecule.
 STRESS CORROSION
STRESS CORROSION CRACKING

Materials are subjected to corrosive attack in to the grain boundaries

where ever that material is placed made tensile stress.

Example: landing gear of an airplane as its on the tarmac.

Landing gear is under stress and that stress is transferred to various parts
of the metal parts.

Parts undergo tensile stress. This result can be sudden and catastrophic
cracking and failure of the metal.
 CREVICE CORROSION

Crevice corrosion is a localized corrosion :

overlapping zones for riveting, bolting or welding, zones under joints

and under various deposits.

These zones also called crevices, are very tiny and difficult to access
for the aqueous liquid that is covering the rest of the readily
accessible surfaces.

This type of corrosion is also known as deposit attack.

VI. CREVICE CORROSION
Stainless steel with bolt with washer on it.
Corrosion has been noticed underneath the washer.
Crevice has been created under the washer.
Stagnant water, an electrolyte, accumulated in the crevice.
The electrochemical, corrosion cell has been produced and corrosion
has resulted.
This cell is called a differential aeration or oxygen concentration cell.
It results because of the difference in the composition of the
electrolyte under the washer and that outside of the washer.
There is a higher oxygen concentration in the solution that surrounds
than washer that there is under the washer.
It is an oxygen concentration cell.
In the ae of a crevice/pit, there are two oxygen concentrations in the
electrochemical cell that has formed.
Thermodynamics is such that corrosion takes place at the lower
oxygen concentration.
EROSION CORROSION

Corrosion by erosion occurs in moving media. This type of corrosion is

related to the process of moving a corrosive liquid against a metal
surface, leading to the accelerated loss of material.

Erosion corrosion also refers to the repetitive formation (corrosion) and

destruction (mechanical process) of the metal’s protective surface film.

It leads to local thinning of the metal, which results in scratches, gullies,

and undulations, which are always oriented in the same direction,
namely the flow direction.

Example: copper water tubes in a hot, high velocity, soft water

environment.

Cavitation is a specific form of erosion corrosion.

 FACTORS AFFECTING CORROSION
NATURE OF THE METAL
Oxidation potential

Over voltage

Relative areas of anode and cathode

Purity of metal

Physical state

Nature of surface film

Passive character

Solubility of corrosion products

Volatility of corrosion products

 FACTORS AFFECTING CORROSION
NATURE OF THE METAL - OXIDATION POTENTIAL

Corrosion depends on the position of the metal in the electrochemical and

galvanic series.

When two metals are in electrical contact in presence of an electrolyte,

The metal higher up in the galvanic series becomes anodic and suffers
corrosion.

The more the two metals are apart in the galvanic series, the greater will
be the corrosion of the anodic metal.
 FACTORS AFFECTING CORROSION

NATURE OF METAL - OVERVOLTAGE

The metal (Zn) higher up in the galvanic series is placed in 1N H2SO4, it

undergoes corrosion forming a film and evolving hydrogen gas.

The initial rate of reaction is quite slow, because of high overvoltage of

zinc metal (0.76V), which reduces the effective electrode potential to a
small value.

However, if a few drops of copper sulphate are added, the corrosion rate
of zinc is accelerated, because some copper gets deposited on the zinc
metal, forming minute cathodes, where hydrogen overvoltage is only
0.33V.

Reduction in overvoltage of the corroding metal alloy accelerates the

corrosion rate.
 FACTORS AFFECTING CORROSION
NATURE OF METAL – RELATIVE AREAS OF ANODE AND CATHODE
Two dissimilar metals/alloys are in contact, corrosion of the anodic part is
directly proportional to the ratio of the cathodic part ad the anodic part.
Corrosion of the anode is directly proportional to the area of the cathode.
Although the corrosion current is same at both cathode and anode, the
current density at the small anode will be much greater and the demand for
electrons can be met by smaller anodic areas only by undergoing corrosion
more briskly.
NATURE OF METAL – PURITY OF METAL
Impurities in a metal, causes heterogenity ad form minute/tiny
electrochemical cells and the anodic parts get corroded.
Example:
Impurities such as Pb/Fe/C in zinc lead to the formation of tiny
electrochemical cells at the exposed part of the impurity and the corrosion
of zinc around the impurity takes place due to local action.
 FACTORS AFFECTING CORROSION
NATURE OF METAL – PHYSICAL STATE OF THE METAL
Rate of corrosion is affected by the physical state of metal.
The smaller the grain size of the metal or alloy, the greater will be its
solubility and hence greater will be its corrosion.
NATURE OF METAL – NATURE OF SURFACE FILM
In aerated condition, most metals get covered with a thin surface film of
metal oxide having a thickness of a few angstroms.
The film may contain one or more forms of the metal oxide and its thickness
depends upon the nature of the metal and temperature.
The ratio of the volumes of the metal oxide to the metal –SPECIFIC
VOLUEME RATIO
Greater the specific volume ratio, lesser is the oxidation corrosion rate. S
The specific volume ratios for W,Cr and Ni are 3-6, 2-0and 1-6 respectively
which indicates that the rate of oxidation at elevated temperatures is least
for W.
 FACTORS AFFECTING CORROSION
NATURE OF METAL – PASSIVE CHARACTER FOR METAL
Metals like Tl, Al, Cr, Mg, Ni and Co are passive and they show much higher
corrosion resistance than expected from their position sin galvanic series,
due to the formation of highly protective, but very thin film (of oxide) on
the metal/alloy surface.
Moreover, the film is of such a self healing nature, that if broken, it repair its
itself, on re-exposure to oxidizing conditions.
Thus, corrosion resistance of stainless steel is due to the passivating
character of chromium present in it.
NATURE OF METAL – SOLUBILITY OF CORROSION PRODUCTS
If the corrosion product is soluble in the corroding medium, then corrosion
proceeds at a faster rate.
If the corrosion product is insoluble in the medium or its interacts with the
medium to form another insoluble product.
PbSO4 formation in case of Pb in H2SO4 medium, then the corrosion product
acts as a physical barrier, thereby suppressing further corrosion.
 FACTORS AFFECTING CORROSION
NATURE OF METAL – VOLATILITY OF CORROSION PRODUCTS
If the corrosion product is volatile, it volatilizes as soon as it is formed,
thereby leaving the metal surface exposed for further attack.
This causes rapid and continuous corrosion, leading to excessive corrosion.
Example: molybdenum oxide (MoO3) is the oxidation corrosion product of
Mo in volatile.
 FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – TEMPERATURE
The rate of chemical reactions and rate of diffusion increase with
temperature and polarization decreases.

Corrosion increases with temperature.

FACTORS AFFECTING CORROSION

NATURE OF ENVIRONMENT – PRESENCE OF MOISTURE
Humidity in air affect atmospheric corrosion.

Critical humidity: relative humidity above which the atmospheric corrosion

rate of metal increases sharply.

Critical humidity value depends on the physical characteristics of the metal

and corrosion products.

Metal corrodes faster in humid atmosphere (CO2, O2 etc and vapours)

Is essential for setting up an electrochemical cell.
 FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – PRESENCE OF IMPURITIES IN ATMOSPHERE
Corrosive gases like CO2, H2, SO2 and fumes of HCl, H2SO4 etc.

In presence of these gases, the acidity of the liquid adjacent to the metal
surfaces increases and its electrical conductivity also increases, thereby
corrosion is increased.
FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – SUSPENDED PARTICLES IN ATMOSPHERE
If suspended particles are chemically active in nature [NaCl, (NH4)2SO4 } they
absorb moisture and act as strong electrolytes, thereby causing increased
corrosion.

If suspended particles are chemically inactive in nature (charcoal can absorb

both sulphur gases and moisture and slowly increases the corrosion rate.
 FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – EFFECT OF pH
Acidic media are generally more corrosive than alkaline or neutral media.
Amphoteric metals (Al,Zn,Pb) dissolve in alkaline solution as complex ions.
The corrosion rate of Fe in oxygen free water is slow, until the pH is below
5.0.
The corresponding corrosion rate in presence of oxygen is much higher.
Corrosion of metals, readily attacked by acid, can be reduced by increasing
the pH of the attacking environment.
Example: Zinc (which rapidly corroded even in weakly acidic solutions such
as carbonic acid) suffers minimum corrosion at pH = 11.
FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – NATURE OF IONS PRESENT
Chloride ions present in the medium destroy passive film and corrode man
metals/alloys.
The presence ofanions like silicates in the medium leads to formatin of
insoluble reaction products eg. Silica gel, which inhibits further corrosion.
 FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – CONDUCTANCE OF THE MEDIUM
Conductance of dry sandy soils is lower than those of clay and mineralized
soils.
Stray currents (from power leakages) will cause more severe damage to the
metallic structures buried under clay and mineralized soils than those under
dry sandy soils.
FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – CONCENTRATION OF OXYGEN AND
FORMATON OF OXYGEN CONCENTRATION CELL
The rate of corrosion increases with supply of oxygen.
Less oxygen concentration, example: oxide coated part of less exposed parts
becomes anodic, more oxygenated regions or parts more exposed to oxygen
become cathodic.
This leads to the formation of oxygen concentration cell in which anodic
part suffers from oxidation
At cathode: 2H2O + O2 + 4e-  4OH-
At anode: Fe  Fe2+ + 2e-
 FACTORS AFFECTING CORROSION
NATURE OF ENVIRONMENT – FLOW VELOCITY OF PROCESS STREAM
Since corrosion is controlled by polarisation (i.e slowing down of the
reactions) at the anodes and cathodes.
When a metal that does not passivate, is under diffusion control.
Increasin flow velocity of the medium enhances diffusion rate, therey
increasing the corrosion rate.

In non-passivating type of corroding metals, minimization of flow velociy

may decrease the corrosion rates.