Module - IV

CORROSION
and its CONTROL

Dr. M.Akhila Maheswari

CORROSION
Corrosion is defined as the gradual
destruction or deterioration of
metals or alloys by the chemical or
electrochemical reaction with its
environment.
Corrosion is a surface
phenomenon. It is an oxidation
reaction.
Corrosion
(Oxidation)

metallic compounds + Energy

Metal

Extraction of

 Combined forms are reduced to their metallic states from

their ores extraction process
The isolated pure metals excited state (high energy state)
than their corresponding ores

They have a natural tendency to revert back to combined

state (low energy state)
When the metals put into use exposed to environment
(dry gases, moisture, liquids), the exposed metal surfaces
begin to decay conversion into more stable metal
compounds
Destruction or deterioration of the metal starts at the
surface

CLASSIFICATION OF CORROSION
Based on the environment, corrosion is classified in to
1. Dry or Chemical corrosion
2. Wet or Electrochemical corrosion.
Dry or Chemical corrosion (absence of moisture):
Dry corrosion is due to the attack of metal surfaces by
the atmospheric gases such as oxygen, hydrogen
sulphide, sulphur dioxide, nitrogen, inorganic liquids
etc.
There are three main types of dry corrosion;

1. Oxidation corrosion (or) corrosion by oxygen

2. Corrosion by hydrogen.
3. Liquid metal corrosion.
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OXIDATION CORROSION

Oxidation corrosion is brought about by the direct

attack of oxygen at low or high temperatures on
metal surface in the absence of moisture.

Alkali metals like (Li, Na, K, etc) and alkaline-earth

metals (Mg, Ca, Sr, etc) are rapidly oxidized at low
temperature.

At high temperature, almost all metals (expect Ag,

Au and Pt) are oxidized.

MECHANISM OF DRY CORROSION

Oxidation occurs first at the surface of the metal
resulting in the formation of metal ions (M2+), which
occurs at the metal/oxide interface.
Anodic (Oxidation) Reaction:

M2+ +2e-

Cathodic (Reduction) Reaction:

Oxygen changes to ionic form (O2-) due to the transfer of electron
from metal, which occurs at the oxide film / environment
interface.
O2 + 2e- O2Overall reaction: Oxide ions reacts with the metal ion to form the
metal- oxide film.
M + O2 M2+ +O2- MO (Metal-oxide film)

NATURE OF OXIDE FILM

The nature of oxide film formed on the metal surface plays in
important role in oxidation corrosion.

(i) STABLE OXIDE LAYER

A stable oxide layer behaves as a protective coating and no further
corrosion can develop.
Example: oxides of Al, Sn, Pb, Cu, etc., are stable oxide layers.

(ii) UNSTABLE OXIDE LAYER

Unstable oxide layer is mainly produced on the surface of
noble metals, which decomposes back in to the metal and
oxygen.
Metal oxide Metal +Oxygen
Example: Oxides of Pt, Ag, etc., are unstable oxide layers.
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(iii) VOLATILE OXIDE LAYER

The oxide layer volatilizes as soon as it is formed, leaving the
metal surface for further corrosion.
Example: Molybdenum oxide is volatile.
(iv) POROUS OXIDE LAYER
Metal oxides having pores and cracks allow penetration of
oxygen to the underlying metal, resulting in the complete
conversion of metal into its oxide. Continues till the entire
metal is completely converted into its oxides

Example: Iron, alkaline-earth metals

PILLING BEDWORTH RATIO

The ratio of the volume of the oxide formed to
the volume of the metal consumed is called
pilling-bedworth ratio.

R = Md/nmD
Where M - mass of metal oxide
m - atomic weight
d - density of the metal
D - density of the scale
n- number of metal atoms in a formula of the scale
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PILLING-BEDWORTH RULE
According to PillingBedworth rule,
1. If the volume of the oxide layer formed is less than the volume of the metal,
the oxide layer is porous and non-protective.
Example: Oxides of alkali and alkaline earth metals.
PB < 1 tensile stresses in oxide film brittle oxide cracks
2. If the volume of the oxide layer formed is greater than the volume of the
metal, the oxide layer is subjected to cracking and spalling resulting in poor
oxidation resistance and protection.
Example: Oxides of heavy metals such as Fe, Sb, V, W, etc.
PB >> 1 too much compressive stresses in oxide film oxide cracks
3. If the volume of oxide layer is equal to the volume of the metal then there will
be protective oxide film formation.
Example: Oxides of Al, Sn, Pb, etc.
PB > 1 compressive stresses in oxide film uniformly cover metal
surface and is protective
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CORROSION BY OTHER GASES

Gases like SO2, CO2, Cl2, H2S etc induce corrosion

action on metals

Corrosion effect depends on the chemical affinity

between the metal and the gas.

The degree of attack by gases depends on the formation

of protective or non-protective films on the metal
surface.

(1)

If the film is non-porous or protective, the intensity of

attack decreases. Eg. AgCl film attack of Cl2 on Ag

(2)

If the film is porous or non-protective, the surface of the

whole metal is gradually destroyed.
Eg. Dry Cl2 gas attack on Sn formation of volatile SnCl4
fresh surface is exposed for further attack
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CORROSION BY HYDROGEN- HYDROGEN

EMBRITTLEMENT
Contact of metal with H2S results in the generation of
atomic hydrogen
E.g. Fe + H2S FeS + 2H
H + H
H2
Corrosion caused by the exposure of metal to hydrogen
environment.
Hydrogen in atomic state diffuses into the metal matrix
and collects in the voids present in the metal.
The hydrogen atoms combine to form H2 gas.
A very high pressure is developed, which results in cracks
and blisters on metal. This process is called hydrogen
embrittlement.
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DECARBURISATION
At higher temperature atomic hydrogen is formed by the
thermal dissociation of molecular hydrogen.

H2 2H
When steel is exposed to this environment, the atomic
hydrogen readily combines with carbon of steel and
produces methane gas.
C + 4H CH4
Collection of these gases in the voids develop very high
pressure, which causes cracking. Thus the process of
decrease in carbon content in steel is termed as
Decarburisation of steel.
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LIQUID - METAL CORROSION

This is due to the chemical action of flowing liquid metal at
high temperature.
The corrosion reaction involves either,
(i)

Dissolution of a solid metal by a liquid metal

(or)
(ii)

Liquid metal may penetrate in to the solid metal.

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WET (or) ELECTRO-CHEMICAL

CORROSION

Most of the corrosion processes

are electrochemical in nature

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WET (or) ELECTRO-CHEMICAL

CORROSION
Wet corrosion occurs under the following
conditions,
When two dissimilar metals are in contact
with each other in the presence of an

aqueous solution or moisture.

When two
metal are

dissimilar parts of the same

in contact with an aqueous
solution of an electrolyte.

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MECHANISM OF WET CORROSION

According to electrochemical theory of corrosion,
the wet corrosion involves two steps.
a) Oxidation or metal dissolution
b) Reduction
Metal dissolution occurs always at anode leading to
the formation of metal ions and electrons

M Mn+ + neAt cathode, electron consumption resulting in either

evolution of hydrogen or absorption of oxygen
depending on the nature of corrosion environment.
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(a) Acidic environment

If the corrosive environment is acidic, hydrogen evolution occurs at
cathodic part.
2H+ + 2e- H2

(b) Alkaline or Neutral environment

If the corrosive environment is slightly alkaline (or) neutral,
hydroxide ion forms at cathodic part.
O2 + 2e- +H2O 2OHThus the metal ions (from anodic part) and non-metallic ions (from
cathodic part ) diffuse towards each other through conduction
medium and form a corrosion product between anode and
cathode.
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a) Hydrogen evolution type corrosion

Metals having negative reduction potential i.e., below hydrogen

reduction potential value in the electrochemical series get

dissolved in acidic solution with simultaneous liberation of
hydrogen gas.
Example: Iron metal in contact with non-oxidizing acid like HCl
results in H2 evolution
At anode: Iron (Fe) undergoes dissolution to Fe2+ with the
liberation of electrons.
At cathode: The liberated electrons follow from anode to
cathode, where H+ ions get reduced to H2.

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21

b) Absorption of oxygen or formation of hydroxide ion

type corrosion
Fe surface usually contains a coating of Iron oxide and if this oxide layer

develops, cracking happens.

As a result anodic areas are created on the surface and remaining area acts
as cathode.
Example: Iron metal in contact with a neutral solution of electrolyte in the
presence of O2, OH- ions are formed.
At anode: Iron (Fe) undergoes dissolution to Fe2+ with the liberation of
electrons.
At cathode: The liberated electrons follow from anode to cathode, where
dissolved O2 is consumed to form OH- ions.

1/2O2 + H2O + 2eFe2+ + 2OHFe(OH)2 + 2H2O + O2

2OHFe(OH)2
4Fe(OH)3 (rust)
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Absorption of oxygen
Rusting of iron in neutral aqueous solution of
electrolytes in the presence of oxygen
At anodic area:

Fe Fe2+ +2eAt cathodic

area:

O2 + H2O + 2e- 2OH-

Fe2+ + 2OH- Fe(OH)2

Enough
Oxygen:

4 Fe(OH)2 +O2+ 2H2O 4 Fe(OH)3

Reason for corrosion product formation at cathode

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Yellow
rust:

4Fe(OH)3
(2Fe2O3. 6H2O)

Fe2O3.H2O
Smaller Fe2+ diffuse more rapidly than OHcorrosion occurs at the anode
rust is deposited at or near cathode

Oxygen is
limited:
Black
anhydrous
magnetite

Fe3O4
Fe2+Fe23+O4
FeO.Fe2O3

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Chemical Corrosion
It occurs only in dry condition

Electrochemical Corrosion
It occurs in the presence of
moisture or electrolyte

It is due to the direct chemical It is due to the set up of a

attack of the metal by the
large number of cathodic and
environment
anodic areas
Even a homogeneous metal
surface gets corroded

Hetergeneous surface or
bimetallic contact is required
for corrosion

Corrosion products
accumulate in the same place,
where corrosion occurs.

Corrosion occurs at the anode,

while products formed
elsewhere

Chemical corrosion is selfcontrolled

It is continuous process

It follows adsorption
It follows electrochemical
mechanism
reaction
Eg. Formation of mild scale on Eg. Rusting of iron in moist
iron surface
atmosphere

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Standard Potentials at Electrode Reactions at 25 0C

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Types of wet / Electrochemical corrosion

Galvanic corrosion
Concentration corrosion
Differential metal ion concentration: METAL ION
CONCENTRATION CELL
Differential areation corrosion OXYGEN CONCENTRATION
CELL
Crevice corrosion
Pitting corrosion
Water line corrosion

Stress corrosion cracking

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GALVANIC CORROSION
When two different metals are in contact with each other
in the presence of an aqueous solution or moisture,
galvanic corrosion occurs. Here, the more active metal
(with more negative electrode potential) acts as anode and
the less active metal (with less negative potential) acts as
cathode.

Example for galvanic corrosion

Steel screw in a brass marine hardware corrodes. This is
due to galvanic corrosion. Iron (higher position in
electrochemical series) behaves anodic and is attacked
and corroded, while brass (lower in electrochemical series)
acts as cathode and is not attacked.

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Bolt and nut made of the same metal is preferred.

Why?
It is preferred in practice, because galvanic
corrosion is avoided due to homogeneous metals (no
anodic and cathodic part).
Prevention:
1. Avoid unfavorable area effect
2. Selection of metals & alloys
3. Insulating dissimilar metals
4. Using inhibitors
5. Applying cathodic protection

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Galvanic or Bimetallic or Differential

metal corrosion
When two dissimilar metals (example: zinc and copper)
are electrically connected and exposed to an electrolyte
The metal higher in electrochemical series undergoes
corrosion
This type of corrosion is called galvanic corrosion
Zinc higher in electrochemical series forms the anode
and is attacked and gets dissolved
Copper - lower in electrochemical series acts as cathode

Zn Zn2+ + 2e31

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33

Galvanic corrosion
1. Also called ' dissimilar metal corrosion Differential metal corrosion.
2. Takes place when two metals are in physical contact with each other and are
immersed in a conducting fluid.
3. corrosion damage induced when two dissimilar materials are coupled in a
corrosive electrolyte.
4. Examples:
1. Plate and screw of different electrical potentials due to differences in
processing
2. Multiple component implant using different metals for each
component
3. Copper and steel tubing are joined in a domestic water heater, the
steel will corrode in the vicinity of the junction
5. The following fundamental requirements have to be met for galvanic corrosion:
1. Dissimilar metals (or other conductors, such a graphite).
2. Electrical contact between the dissimilar conducting materials (can be
direct contact or a secondary connection such as a common
grounding path).
3. Electrolyte (the corrosive medium) in contact with the dissimilar
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conducting materials.

Galvanic corrosion between

stainless steel screw and
Aluminium.

Galvanic corrosion between

Steel and Brass.

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Factors of galvanic corrosion

Difference between the electrode potentials of the two metals Greater
the difference greater the corrosion.
Contact resistance at the boundary between the two metals - Higher the
contact resistance lesser the corrosion rate.
Electrical resistance of electrolytes lower the concentration of the
electrolyte higher the resistance lower the corrosion rate.
Anode-to-cathode ratio: Large anode connected to small cathode - lower
corrosion rate.
Presence of a passive film
Electrolyte solution properties pH, Oxygen content, temperature, flow
rate.
Examples to show this kind of corrosion:

Steel pipe connected to copper

Zinc coated on mild steel
Tin coating on copper vessel
Lead-Antimony solder around copper wires
Important slide 36

Galvanic Series
Electrochemical series only for pure metals
Reduction potential arranged down in an increasing order

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Galvanic Series

Cu+Zn

Nickel alloy
(Ni, Cu,38Fe)

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1. In the Galvanic series, a metal high in the series is

more anodic and undergoes corrosion faster than
below it
For example: Zn corrodes faster than Fe

2. It accounts for the corrosion of all metal & metal

alloys
3. It is more practical series

4. It gives the real and useful informations for studying

the corrosion of metals and alloys
It has been prepared by studying the corrosion of
metals and alloys in a given environment

For example: sea-water

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Concentration Cell Corrosion or

differential aeration

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Examples for differential aeration

corrosion

Pitting or localized corrosion

Crevice corrosion
Soil corrosion
Fencing Corrosion
Waterline Corrosion

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Due to electrochemical attack on the metal

surface when it is exposed to an electrolyte of
varying concentrations or of varying aeration

Differential aeration corrosion occurs when

one part of metal surface is exposed to
differential air concentrations or oxygen
concentrations from the other part

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The part of the metal exposed to higher oxygen

concentration acts as cathodic region and part of the
metal exposed lower oxygen concentration acts as
anodic region. Consequently, poorly oxygenated
region undergoes corrosion.
n+
At anode
n
e
M
M +

O2 + H2O + 2e- 2OH-

At cathode

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Drops of water or salt

solution

Fe2
+

45

At anode (less aerated) corrosion occurs

M M2+ +2eAt cathode (more aerated part) OH- ions are produced
O2 +H2O + 2e- 2 OH46

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Facts about differential aeration corrosion

1. Corrosion is accelerated in apparently inaccessible places
because the oxygen deficient areas serve as anodes
cracks or crevices serve as foci for corrosion
2. Corrosion is accelerated under accumulation of dirt sand,
scale or other contamination restricts the access of oxygen
and establishes an anode to promote greater accumulation

Localized corrosion and non-uniform corrosion

3. Metals exposed to aqueous media corrode under blocks of
wood or piece of glass which screen that portion of metal
from oxygen access

4. More intensified with the time

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Passivity or Passivation
It is the phenomenon in which a metal or an alloy exhibits a much
higher corrosion resistance than expected from its position in the
electrochemical series.
Passivity is due to the formation of a highly protective thin layer
being formed on the surface of that metal.
This film is non-porous, insoluble and resistant to corrosive
atmosphere.
Self healing nature broken repair itself
Passivity is not a constant state, but exists only in certain
environment conditions which tend to maintain thin protective
oxide films on their surface.
Presence of oxygen oxide film automatically repair damage
In the absence of oxygen chemical active rapidly corroded
Examples of passive metals and alloys are Ti, Al, Cr and some
alloys of steels containing these metal systems.
Alloy : More corrosion resistant than metal
Thin film (Invisible 0.0004 mm thick) : Resistance

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Stainless steel (Fe and Cr alloy)

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Pitting corrosion
1. Pitting corrosion is a localized form of corrosive attack that
produces holes or small pits in a metal.
2. the bulk of the surface remains unattacked.

3. Pitting is often found in situations where resistance against

general corrosion is conferred by passive surface films.
4. Localized pitting attack is found where these passive films have
broken down.
5. Pitting can be one of the most dangerous forms of corrosion
because it is difficult to anticipate and prevent, relatively
difficult to detect, occurs very rapidly, and penetrates a metal
without causing it to lose a significant amount of weight.

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Pitting corrosion

Once a pit is formed, the rate of corrosion increases.

This is because of the formation of small anodic area (pit)
compared to a large cathodic area (surface)
The latter induces the small anodic area to corrode faster
by accepting electrons from the anodic are resulting in the
enlargement of the pit
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53

Crevice corrosion
If a crevice between different metallic objects or
between metal and non-metallic material is in
contact with liquids, the crevice becomes the anodic
region and suffers corrosion.
This is due to less oxygen with crevice area.
The exposed areas act as the cathode.

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PIPELINE CORROSION
Differential aeration corrosion may also
occur in different parts of pipeline.
Buried pipelines or cables passing from one
type of soil to another, example from clay
(less aerated) to sand (more aerated) may get
corroded due to differential aeration.

55

CORROSION ON WIRE-FENCE
A wire fence in which the areas where the wires cross are
less aerated than the rest of the fence and hence corrosion
occurs at the wire crossings, which are anodic.
Other examples for differential aeration corrosion
(i) Corrosion occurring under metal washers, where oxygen
cannot diffuse easily.
(ii) Lead pipeline passing through clay to cinders undergo
corrosion. Since the pipeline under cinders is more aerated,
therefore gets corroded easily.

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Stress Corrosion/Cracking
Combined effect of tensile stress and corrosive environment
Ex : Cu in Ammonia solution, mild steel in Strong nitrate, caustic

alkalis.
Stress is caused due to heavy working like rolling, drawing or
insufficient annealing.
It occurs along narrow paths and not on the surface.
The presence of stress produces strains thus resulting in localized

zones of high electrode potential.

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Stress Corrosion Cracking (SCC)

Stress corrosion:
In a metallic structure, if there is a portion under stress, it will
act as anode and rest part of the structure will act as cathode.
Spontaneous corrosion induced cracking of a material under
static (or residual) tensile stress.

It is now a galvanic system and hence anodic part which is

small in area will corrode more.
Stress corrosions are observed in the different systems- Two
classic examples of SCC

Caustic embrittlement
Season cracking - Only specific environment cause
failure
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Cracks grow along grain boundaries as a result of residual or

applied stress or trapped gas or solid corrosion products

59

Crack Propagation
Transgranular
Crack
propagating
across grains
Grains

Metallic
Grains

Crack
propagating
along metallic
grain
boundaries

Intergranular

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Transgranular mode

Intergranular mode

Stress corrosion cracking in Stainless steel

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Stress Corrosion Cracking (SCC)

62

Caustic embrittlement
A type of stress corrosion occurring in steel tank (Boiler)
at high temperature and in alkaline medium.
Boiler water has Na2CO3; it will be hydrolyzed at high
temperature to give NaOH.
It flows into hair cracks and crevices. There it reacts with
iron and forms Na2FeO2 (sodium ferroate) which
decomposes to give Fe3O4 (ferroferric oxide FeO.Fe2O3)
and NaOH.
NaOH thus formed further reacts with iron to cause
corrosion. It is called caustic embrittlement.
Addition of Na2SO4 to boiler water in addition to tannin and
lignin to boiler water prevents caustic cracking.
By neutralization of excess of alkali with dilute acid (or)
control of pH value caustic embrittlement can be controlled.
63

Season cracking
It is applied to stress corrosion of copper alloys.
Pure copper metal is less sensitive to stress corrosion.
However, presence of alloying impurities like P, Zn, Al, etc.
results in marked sensitivity for corrosion.
Some of the alloys like brass are made of zinc and copper.
In the presence of ammonia or amines, induces season
cracking in zinc and copper
These metals form complexes [Cu(NH3)4]++ [Zn(NH3)4]++ which
appear as corrosion products.

64

Stress corrosion may be reduces:

1. By applying protective coatings
2. Using corrosion inhibitors
3. By stress relief heat treatments

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