6.

CORROSION
TYPES OF CORROSION-
The process of corrosion of metals
depends on the environment to which
the metals are exposed. The corrosion
of metals can be of two types:
1. Dry corrosion
2. Wet corrosion
1.DRY CORROSION OR
CHEMICAL CORROSION OR
DIRECT CHEMICAL ATTACK

 Dry corrosion involves direct attack of atmospheric

gases on metal in the absence of moisture liquid
phase. The corrosive media include gases like
oxygen, halogens, oxides of sulphur, nitrogen,
hydrogen sulphide.
 There are three main types of dry corrosion.

1.Oxidation corrosion (reaction with oxygen).

2.Corrosion by other gases (such as Cl2, SO2, H2S,
NOx).
3.Liquid metal corrosion.
A)Oxidation corrosion
(Reaction with oxygen):
Metals are attacked by dry oxygen
at extreme conditions like low or
high temperature leading to
oxidation type of corrosion. The
alkali and alkaline earth metals are
more prone and rapidly oxidised at
low temperature, while metals like
Fe, Al etc. (except noble metals)
are oxidised at high temperature
by the interaction with oxygen.
Mechanism-
 Metal oxide formation takes place in the
following steps:
• First the oxygen molecule gets adsorbed
on metal surface.
• Oxygen molecule get atomized (i.e.
dissociation of O2 molecule into atoms).
• Metal being electropositive, loss of
electrons takes place by metal atom to oxygen
atom.
• Thus, the metal oxide layer is formed
perpendicular to the metal surface and forms a
barrier for reaction of further metal atoms with
the oxygen in the air.
Types of Oxide Films
1.Stable or Protective or Non-porous oxide layer:
It is fine-grained film that adheres well to the
metal layer forming a kind of protective coating. It is
non-porous or impervious in nature and prevents
further oxidation of metal. Such a film behaves as
protective coating in nature, thereby shielding the
metal surface. Metals like Cr, Al, Sn, Pb, Cu etc. forms
oxides whose volumes are greater than the volume of
metal exposed and hence no pore and cracks on the
oxide layer. Thus stable or protective layers is formed.
Consequently, further oxidation corrosion is prevented.
 2Al + O2 ⎯→ Al2O3
 2Cu + O2 ⎯→ 2CuO
 4Cr + 3O2 ⎯→ 2Cr2O3
2. Porous or Non-protective oxide film
or layer:
 Metals like Na, Mg, Fe, K, Ca etc etc.
forms oxides having less volume than the
volume of metal exposed. Hence, the oxide
layer formed having pores or cracks. The
atmospheric oxygen have access to travel to
inner layer of metal, thereby corrosion
continues unobstructed, till the entire metal
is completely converted into its oxide.
 e.g. 4Na + O2 ⎯→ 2Na2O
 2Fe + O2 ⎯→ 2FeO
 2Mg + O2 ⎯→ 2MgO
3. Unstable oxide layer:
The oxide film formed, decomposes
back to metal and oxygen, so no oxidation
corrosion is observed for these metals.
e.g. Ag, Au and Pt.
4Ag + O2 2Ag2O
4. Volatile oxide film or layer:
The metal oxide formed volatizes as
soon as it is formed, exposing a fresh layer
of metal for oxidation, resulting in rapid
corrosion. e.g. Mo.
4Mo + 3O2 ⎯→ 2Mo2O3 ↑
B)Corrosion by other gases such as Cl 2, SO2, H2S,
NOx:
In dry atmosphere, these gases react with metal and
form corrosion products, which may be protective or
non-protective.
Dry Cl2 reacts with Ag and forms AgCl which is a
protective layer, while SnCl4 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:
In several industries, molten metal passes through
metallic pipes and cause corrosion due to dissolution or
internal penetration. For example, liquid metal mercury
dissolves most metals by forming amalgams, thereby
corroding them.
 WET CORROSION
(ELECTROCHEMICAL CORROSION)
Wet corrosion usually occurs in
conducting liquid phase through
electrochemical reaction.
This type of corrosion occurs when
the metal comes in contact with a
conducting liquid or when two
dissimilar metals are immersed or
dipped partly in a solution. In other
words, wet corrosion involves
electrochemical attack on metals in
aqueous environments.
 The reactions involved in the Galvanic cell are as follows:
1.Anodic reaction: Metal undergoes oxidation with release of
electrons.
Fe ⎯→ Fe2+ + 2e−
2.Cathodic reaction: At the cathodic region, electrons are
absorbed and cause reduction of constituents. There are
following possible ways in which reduction takes place.

If the solution is aerated and almost neutral, oxygen is reduced

in the presence of H2O to OH− ions.
O2 + 2H2O + 4e− ⎯→ 4OH−
If the solution is aerated and acidic in nature
4H+ + O2 + 4e− ⎯→ 2H2O
If the solution is de-aerated and almost neutral, then H 2 is
liberated along with OH− ions.
2H2O + 2e− ⎯→ H2 ↑ + 2OH−
If the solution is deaerated and acidic, H+ ions are reduced to
hydrogen gas.
2H+ + 2e− ⎯→ H2 ↑
A. Hydrogen evolution
mechanism:
 This type of corrosion occurs, usually in acidic environment.
Considering metal like (steel) iron tank is in contact with
other metal like copper in acidic medium, give rise to an
electrochemical cell.
In this cell, steel acts as anode and copper acts as cathode.
The anodic reaction is dissolution of iron as ferrous ions with
the liberation of electrons.
At anode:
Fe ⎯→ Fe2+ + 2e− (oxidation)
These electrons flow through the metal, from anode to
cathode, where H+ ions (of acidic solution) are eliminated as
hydrogen gas.
At cathode:
2H+ + 2e− ⎯→ H2 ↑ (reduction)
The overall reaction is
Fe + 2H+ ⎯→ Fe2+ + H2 ↑
B)Oxygen absorption mechanism:

Rusting of iron in neutral aqueous solution

of electrolytes in the presence of
atmospheric oxygen is a common example
of this type of corrosion.
The surface of iron is usually coated with a
thin film of iron oxide. However, if this iron
oxide film develops some cracks, anodic
areas are created on the surface; while the
metal oxide layer act as cathode. It follows
that the anodic areas are small surface
parts, while nearly the rest of surface of
the metal forms large cathodes
 At the anodic area the metal dissolves as ferrous
ions with liberation of electrons.
Fe ⎯→ Fe2+ + 2e− (oxidation)
 These liberated electrons flow from anodic to
cathodic areas.
O2 + H2O + 2e− ⎯→ 2OH−
 Fe++ ions (at anode) and OH− ions (at cathode)
diffuse, ferrous hydroxide is precipitated.
Fe2+ + 2OH− ⎯→ Fe(OH)2 ↓
 If enough oxygen is present, ferrous hydroxide is
oxidised to ferric hydroxide.
4Fe(OH)2 + O2 + 2H2O ⎯→ 4Fe(OH)3
This product, called yellow rust, actually
corresponds to Fe2O3 · H2O.
If the supply of oxygen is limited, the corrosion
product may be even black anhydrous magnetite,
Fe3O4.
 FACTORS INFLUENCING RATE
OF CORROSION
(A) Primary factors:
1. Nature of the metal:
2. Electrode potential difference:
3. Surface state of the metal:
4. Hydrogen over voltage:
5. Formation of protective films
by metals:
(B) Secondary factors:
1. pH:
2. Temperature:
3. Anodic and cathodic area
effect:
4. Conductance of the
medium:
5. Humidity:
METHODS OF CORROSION
CONTROL AND PREVENTION
A)Cathodic Protection
The principle of this method is to “force the metal to
behave as cathode in order to protect it from
corrosion”.
There are two types of cathodic protection: (1)
Sacrificial anodic protection.
(2) Impressed current cathodic protection.
(1) Sacrificial anodic protection:
In this protection method, the metallic structure (to be
protected) is connected by a wire to a more anodic
metal, so that more active metal undergoes corrosion.
As this active metal corrodes itself, thereby cathode
gets protected. It means active metal sacrifices itself
to protect cathode, is called as ‘sacrificial anode’.
The corroded sacrificial anode is replaced by fresh one,
once completely corroded.
Examples of active metals: Magnesium (Mg),
Zinc (Zn), Aluminium (Al) and their alloys
 In this protection, more active metal (anode) uses
electrons in order to protect metal (cathode). The
flow of electrons is increased in the presence of back
fill. Back fill reduces electrical resistivity of the
medium.
Applications :
∙ Method is used to protect the hulls of ship,
water heaters, pipelines, tanks, refineries, etc.
∙ The advantages of sacrificial anode method over
others are they do not need external power source,
are easy to install, the anode and surface require low
voltage and current.
∙ It has few disadvantages including a limited
current capacity based on the mass of anode,
ineffectiveness in high resistivity area.
2)Impressed current cathodic
protection:

 In this method, an impressed current is applied in

opposite direction to nullify the flow of corrosion,
by converting anodic metal into cathodic one.
 An impressed current is induced from direct
current (DC) i.e. battery/rectifier etc. with an
insoluble anode like graphite, high silica iron,
scrap iron, stainless steel, platinum, etc.
In this method, metallic structure to be protected is
connected to an insoluble anode through DC current.
Anode is surrounded by backfill composed of coke,
bronze or gypsum, which increase electrical contact
with the surrounding soil.
It is useful for large structures for long-term
operations.
Application:
∙ It is used for water coolers, buried
oil/water pipelines, condenser, transmission
etc.
 Anodic Protection
Principle:
“The growth of protective oxide film on the surface
of metal/alloy by an application of anodic current in a
suitable oxidizing atmosphere.”
The minimum current density needed to maintain
passivation in the metal/alloy, that potential is called as
passivation potential.
At this potential, minimum corrosion of the
metal/alloy takes place, which makes it passive, thereby
reducing the corrosion rate.
In this method, the metal/alloy (to be protected) is made
anode in a suitable oxidizing medium. The potential is
increased slowly to passivation potential to allow initial
corrosion to take place. Thus, by monitoring the current,
the minimum corrosion takes place, and metal gets
oxidized to form oxide layer on the surface. This oxide
Limitations:
1. During this method, the corrosion takes place
slowly.
2. This method is only applicable to metals/alloys,
which passivate.
Applications:
1. It is used for transportation of chemicals, which
are concentrated in nature.
2.It is also used to carry and transport
METALLIC COATINGS

A coated surface isolates the underlying

metal from the corroding environment, which
may have following limitations. It needs to
overcome as :
1. The coating applied must be
chemically inert at STP.
2. The coating must avoid direct
contact of environment to the base metal.
There are two types of coatings:
(1) Anodic coating
(2) Cathodic coating
 Anodic Coating
It is the coating of metal (on the surface of base
metal), which has higher position in
electrochemical/Galvanic series with respect to
the base metal.
 Examples: Coating of Zn, Al, Cd on
steel.
Since Zn, Al, Cd are in higher
position in electro-chemical series and
steel has lower position.
In case of any pores present in coating, the base metal
gets exposed to an environment. As Zn has higher
position in electrochemical series, it will get consumed
first, then corrosion starts at base metal. Therefore,
base metal gets protected even if it has pores.
Hence, anodic coating scarify to protect base
metal and it is called as sacrificial coating.
Cathodic Coating
It is the coating of metal on the surface
of base metal, which has slightly lower
position in the electrochemical series with
respect to base metal.
Example: Coating of Sn on steel
In case of any pores present in coating, the
base metal gets exposed to an environment.
As Sn has slightly lower position in the
electrochemical series, it allows corrosion of
base metal. Therefore, base metal starts
corroding if any pores are present.
Hence, localized attack at the small
exposed part occurs, resulting in several
pitting and perforation of base metal.
METHODS OF APPLYING
PROTECTIVE COATINGS

Following are the methods of

application of protective
coatings on the surface of base
metal for the protection from
corrosion:
1. Hot 2. 3. 4.
dipping Metal Electroplati Cementati
cladding ng on
 Hot Dipping
 A) Galvanization:
It is the process of coating a thin coat of Zn on the surface
of iron/steel to prevent from rusting.
Galvanization process is carried out by following
steps
1.The iron/steel articles (e.g. sheet, pipe, wire etc.) is first
cleaned by pickling with dil. H2SO4 solution at 60-
90°C for 15-20 minutes.
It removes any scale, rust and impurities present on the
surface of base metal.
2.The article is then washed in washing bath and dried in
drying chamber with the help of hot air.
3.It is then dipped in a bath of molten zinc, maintained at
425°C to 430°C, which is covered with a flux of ZnCl2 and
NH4Cl to prevent oxide formation.
Applications:
1. It is widely used for galvanizing metal sheet.
2. It is used to galvanize house-hold items such
as buckets, tubs, container etc.
3. It is used to galvanize machine parts, tools,
ships, tanks and wires.
4. It is used to galvanize metal pipes and wires.
Tinning:
 It is the process of coating a thin coat of Sn
on the surface of iron/steel to prevent the
corrosion.
The process is carried out by following steps :
1.The article is first cleaned followed by
pickling to remove any rust.
2. It is then washed with water and dried
through hot air.
3. It is then passed through molten tin
maintained at 240°C, through flux.
4. After coating of tin, it is passed through
palm oil, to avoid oxidation of tin.
Applications:
1.It is widely used for steel, copper and
brass sheets.
2.It is used for manufacturing of container
for storing various stuffs like food, oil, ghee,
kerosene etc.
3. IT is used for making cooking utensils and
refrigeration equipment's
Metal Cladding
 It is the process by which a dense,
homogeneous layer of coating metal is
bonded firmly and permanently to the
base metal on one or both sides.
 It is achieved by arranging thin
sheets of the coating metal and the base
metal sheet in the form of sandwich,
which is then passed through rollers,
under the action of heat and pressure.
Due to this, coating metal gets bonded
firmly and permanently to the base
metal.
Example: A plate of duralumin is sandwiched
between two layers of 99.5% pure aluminum. It
is called as ‘Alcad’, which is widely used for
aircraft industry.
The cladding is selected not only for good
resistance but also for providing cathodic
protection.
Electroplating
Itis the process of deposition of
coating metal by passing a direct
current through an electrolytic
solution which contains the
soluble salt of coating metal.
OR
It is the deposition of a metal
by electrolysis, over the surface of
metals, alloys or non-metals.
Reactions:
At anode: The anode dissolves in electrolytic bath to produce
M →
their cations M+n + ne−
Example : Ni → Ni+2 + 2e−2 (for Ni-
plating)
At cathode: The dissolved cations are deposited
on the surface of base metal.
M+n + ne− → M
Example: Ni+2 + 2e− → Ni (for Ni-
plating)
 Applications:
 1. It is used for electrodeposition of gold
or silver to prepare attractive and valuable
materials.
 2. It can also protect surfaces by
covering them, which will be more resistant to
corrosion.
 3. It improves conductivity of metals,
which will be used into electronic components
and integrated circuits.
 4. It beautifies metal.
 5. It can be used to reduce friction,
protect from abrasion and radiation
Cementation / Diffusion
Coating
Itis obtained by heating the base metal in a
revolving drum containing a powder of the
coating metal.
 Alloy is formed due to diffusion of
coating metal into base metal. The thickness
of coating metal is controlled by varying the
time of treatment and temperature.
 This process is suitable for coating small
metal articles of uneven surface and intricate
shapes (like bolts, screw, valves, gauge etc.).
The coating metals used are those which can
form alloy with iron (like Zn, Cr, Al etc.).
Sheradizing:
 Itis the process of cementing Zn powder on the surface
of base metal. Following are the steps involved :
 1. The iron articles to be coated is first cleaned
and then packed with “zinc dust” in a drum.
 2. The drum is then closed tightly, so that
oxidation of zinc is minimum.
 3. The drum is slowly rotated for 2-3 hours with
constant temperature between 350°C to 370°C.
 4. Thereby, Zn gets diffused with iron to form Fe-
Zn alloy at the surface.
 5. Finally, the surface of article is covered with a
thin film of Fe-Zn alloy.
 Application:
 It is used for coating of small articles like bolts,
screws, nuts, threaded parts etc.
 Chromizing:
 It is the process of diffusion of mixture of
chromium powder and alumina into Fe.
1.It is carried out by heating mixture of 55%
chromium powder, alumina and base metal at
about 1300°C - 1400°C for 3 - 4 hours.
2.The use of alumina prevents the coalescence
of chromium articles.
3.The process occurs in following stages :
The corrosion resistance of chromized coatings
correspond to ferrite stainless steel.
Applications:
It is applied for the protection of gas turbine
blades.