At point of contact of Mn+ & O2- metallic oxide will form

Chemistry Assignment & that metal oxide scale forms a barrier

to restrict further oxidation of inside metal. Since size of

- II cation (Mn+) is smaller than anion. Hence cation will

diffuse much faster than the anion through the scale for
continuation of oxidation, it can be possible if the metallic
Name : Ayush Satish Deore oxide barrier is porous.
Roll no : J18IMT632
Nature of Oxide film

Corrosion The Nature of oxide film formed on the metal surface plays
an important role in oxidation corrosion.
Introduction :– 1) Stable oxide layer
Corrosion is a natural phenomenon that converts a refined A stable oxide layer acts as a protective coating and
metal into a more chemically stable form such as an oxide, no further corrosion can occur.
hydroxide or an sulphide. It is the gradual destruction of Examples : oxides of Al, Sn, Pb etc. are stable
materials by chemical or electrochemical reaction with their oxide layers.
environment.
1) Unstable oxide layer
Difference between Corrosion and rusting The oxide layer is mainly produced in the
surface of noble metals, which decomposes
back into metal and oxygen.
Corrosion Rusting e.g. Oxides of Pt, Au, etc. are unstable oxide
Process of deterioration of Part of corrosion and is a layers.
materials as a result of chemical process which
chemical, electrochemical or results in the formation 2) Volatile oxide layer
other reactions. of red or orange coating The oxide layer volatizes as soon as it is
on the surface of metals.
formed, leaving the metal surface for the
Oxides of metal or salts are Only iron oxide is
further corrosion.
formed. formed.
e.g. Molybdenum oxide is volatile.
Occur on different surfaces Occurs on surfaces of
such as wood, metals, etc. iron and its alloys.
Occur when the substance is Occurs when a metal is 3) Porous oxide layer
exposed to air or some exposed to air and Metal oxides having pores and cracks allow
chemicals. moisture. penetration of oxygen to the underlying
Occur in materials like Rust or rusting can affect material, resulting in the complete conversion
polymers and ceramics and only iron and its alloys. of metal into oxide
this type is known as e.g. Rust
degradation.
Pilling Bedworth Ratio
Types of Corrosion :-
The Pilling–Bedworth ratio (P–B ratio), in corrosion of
Chemical or Dry Corrosion metals, is the ratio of the volume of the elementary cell of a
metal oxide to the volume of the elementary cell of the
corresponding metal (from which the oxide is created).
Dry corrosion or chemical corrosion occurs when oxygen in
the air reacts with the metal without presence of a liquid. In On the basis of the P–B ratio, it can be judged if the metal is
this the metal surface is attacked by gases such as : likely to passivate in dry air by creation of a protective oxide
Oxygen, Hydrogen Sulphide, Sulphur Dioxide, Nitrogen, layer.
Inorganic Liquids.
V oxide M oxide x ρmetal
There are three types of Dry Corrosion : RPB = =
 Oxidation Corrosion or Corrosion by oxygen V metal n x M metal x ρoxide
 Corrosion by other gases (SO2, Cl2 )
 Liquid – Metal Corrosion RPB  – Pilling–Bedworth ratio
M  –  atomic and molecular mass
Mechanism Of Dry Corrosion n   – number of atoms of metal per molecule of the oxide
p – density
When a metal is exposed to air it gets oxidised by loosing its
valence electrons & reduction of oxygen takes place. V  –  molar volume

n Pilling Bedworth Rule

M+ x (O+2)  Mn+ + O2-
4
  If the volume of the oxide layer formed is less than
the volume of the metal consumed, the oxide layer
is porous and non-protective.
e.g. Oxides of alkali and alkaline earth metals
 If the volume of the oxide layer formed is greater
than the volume of the metal consumed, the oxide
layer is Protective or non-porous.
e.g. Oxides of heavy metals such as Sb,V, W, etc
 If the volume of oxide layer is equal to the volume
of the metal consumed there will be protective
oxide film formation.
e.g. Oxides of Al, Pb, Ni, Cr etc
Corrosion by other gases
 Corrosion can occur due to other gases such as
Cl2, SO2, H2S, CO2, F2 or NOx
 The extent of corrosion depends upon the chemical
affinity between metal and the gas.
 In dry atmosphere, these gases react with metal and
form corrosion products which may be protective
or non-protective.
o Protective: Intensity or extent of attack
decreases after layer formed.
o Non-protective: Continuous Attack
Corrosion by Hydrogen (H2)
Hydrogen Embrittlement
Hydrogen embrittlement (HE) is a process resulting in a
decrease of the toughness or ductility of a metal due to the
presence of atomic hydrogen.
Hydrogen embrittlement has been recognized classically as
being of two types.
 The first, known as
internal hydrogen embrittlement, occurs when the
hydrogen enters molten metal which becomes
supersaturated with hydrogen immediately after
solidification.
 The second type,
environmental hydrogen embrittlement, results
from hydrogen being absorbed by solid metals.
This can occur during elevated-temperature thermal
treatments and in service during electroplating,
contact with maintenance chemicals, corrosion
reactions, cathodic protection, and operating in
high-pressure hydrogen.
Mechanism of H2 embrittlement
Fe + H2S  FeS + 2H
H + H  H2
Formation of cracks and blisters on metal surface due to
high pressure of H2 gas.
Decarburization
Decarburization is a surface degradation phenomenon in the
forging and heat treating of steels. Decarburization may be
described as a metallurgical process in which the surface of
steel is depleted of carbon, by heating above the lower
critical temperature or by chemical action. Steel forgings are
usually decarburized. This process can happen as a side
effect during a process, or can be performed intentionally.
The amount of carbon contained in a metal influences its
hardness. During decarburization, the carbon diffuses from
the surface of the metal, thus weakening the metal. This
diffusion increases at higher temperatures. The effect of
decarburization not only brings down the strength, but also
increases the shear strain below the metal surface. The
fatigue resistance is decreased while the rate of crack growth
and wear rate is increased.
Mechanism of Decarburization (High temp)
H2  2H
C + 4H  CH4
Absorption of oxygen (or) formation of hydroxide
ion type corrosion
At anode: Iron (Fe) undergoes dissolution to Fe 2+ with
the liberation of electrons.
At cathode: The liberated electrons follow from anode
to cathode, where dissolved O 2 is consumed to form
OH- ions.
1/2O2 + H2O + 2e-  2OH-
Fe2+ + 2OH-  Fe(OH)2
(precipitated on metal surface)
Fe(OH)2 + 2H2O + O2  4Fe(OH)3
(O2 rich environment)
Net reaction:
4Fe + 3O2 + 6H2O  2(Fe2O3.3H2O)
Electrochemical or Galvanic or Wet Corrosion
Also known as electrochemical corrosion. Such type of
corrosion is due to the flow of electron from metal surface
anodic area towards cathodic area through a conducting
solution. This is an common phenomena observed if an
electrochemical cell is produced.
 Mechanism Of Wet Corrosion
The electrochemical nature of corrosion can be
illustrated by the attack of zinc by hydrochloric
acid. When zinc is placed in dilute hydrochloric
acid a vigorous reaction occurs; hydrogen gas is
evolved and the zinc is dissolves forming a solution
of zinc chloride. The reaction is as follows
Zn + 2HCl     ZnCl2 + H2
 From the above equation, it is found that the
chloride ion is not involved in the reaction.
Hence the above equation can be rewritten as
follows
Zn + 2H+     Zn+2 + H2
From this equation when the zinc ion reacts with
the hydrogen ions in the acid solution to form zinc
ions and hydrogen gas. During the reaction, zinc is
oxidized to zinc ions and hydrogen ion is reduced
to hydrogen. The reaction can be divided into two
reactions.
In the above reaction oxidation (Anodic reaction)
Zn    Zn+2 + 2e
The reduction reaction (Cathodic reaction)
2H+ + 2e  H2
An oxidation or anodic reaction is indicated by an
increase in valence or a production of an electron.
A decrease in valence charge or the consumption of
electrons signifies a reduction or cathodic reaction.
During metallic corrosion, the rate of oxidation will
equal to the rate of reduction.
Waterline Corrosion
Waterline corrosion is the case in which a portion of the
metal is always under water. The waterline corrosion takes
place due to formation of differential oxygen concentration
cell. The part of the metal below the waterline is exposed
only to dissolved oxygen while the part above the water is
exposed to higher oxygen concentration of the atmosphere.
Thus, the part below water acts as anode and undergoes
corrosion and the part above waterline is free from
corrosion. A distinct line is formed just below waterline due
to deposition.
E.g. ocean-going ships, water storage steel tanks, etc.
Control of Corrosion
Corrosion can be controlled by following methods: -
I. Metal Type
II. Protective Coating
III. Environmental Measures
IV. Sacrificial Coatings
V. Corrosion Inhibitors
VI. Design Modification
I. Metal Type
One simple way to prevent corrosion is to use a corrosion
resistant metal such as aluminium or stainless steel.
Depending on the application, these metals can be used to
reduce the need for additional corrosion protection.
II. Protective Coatings
The application of a paint coating is a cost-effective way of
preventing corrosion. Paint coatings act as a barrier to
prevent the transfer of electrochemical charge from the
corrosive solution to the metal underneath.
Another possibility is applying a powder coating. In this
process, a dry powder is applied to the clean metal surface.
The metal is then heated which fuses the powder into a
smooth unbroken film. A number of different powder
compositions can be used, including acrylic, polyester,
epoxy, nylon, and urethane.
III. Environmental Measures
Corrosion is caused by a chemical reaction between the
metal and gases in the surrounding environment. By taking
measures to control the environment, these unwanted
reactions can be minimized. This can be as simple as
reducing exposure to rain or seawater, or more complex
measures, such as controlling the amounts of sulphur,
chlorine, or oxygen in the surrounding environment. An
example of this would be would be treating the water in
water boilers with softeners to adjust hardness, alkalinity, or
oxygen content.
IV. Sacrificial Coatings
Sacrificial coating involves coating the metal with an
additional metal type that is more likely to oxidize; hence
the term “sacrificial coating.”
There are two main techniques for achieving sacrificial
coating: cathodic protection and anodic protection.
V. Cathodic Protection
The most common example of cathodic protection is the
coating of iron alloy steel with zinc, a process known as
galvanizing. Zinc is a more active metal than steel, and
when it starts to corrode it oxides which inhibits the
corrosion of the steel. This method is known as cathodic
protection because it works by making the steel the cathode
of an electrochemical cell. Cathodic protection is used for
steel pipelines carrying water or fuel, water heater tanks,
ship hulls, and offshore oil platforms.
VI. Anodic Protection
Anodic protection involves coating the iron alloy steel with
a less active metal, such as tin. Tin will not corrode, so the
steel will be protected as long as the tin coating is in place.
This method is known as anodic protection because it makes
the steel the anode of an electrochemical cell.
Anodic protection is often applied to carbon steel storage
tanks used to store sulfuric acid and 50% caustic soda. In
these environments cathodic protection is not suitable due to
extremely high current requirements.
VII. Corrosion Inhibitors
Corrosion inhibitors are chemicals that react with the
surface of the metal or the surrounding gases to suppress the
electrochemical reactions leading to corrosion. They work
by being applied to the surface of a metal where they form a
protective film. Inhibitors can be applied as a solution or as
a protective coating using dispersion techniques. Corrosion
inhibitors are commonly applied via a process known as
passivation.

VIII. Passivation
In passivation, a light coat of a protective material, such as
metal oxide, creates a protective layer over the metal which
acts as a barrier against corrosion. The formation of this
layer is affected by environmental pH, temperature, and
surrounding chemical composition. A notable example of
passivation is the Statue of Liberty, where a blue-green
patina has formed which actually protects the copper
underneath. Corrosion inhibitors are used in petroleum
refining, chemical production, and water treatment works.

IX. Design Modification

Design modifications can help reduce corrosion and
improve the durability of any existing protective anti-
corrosive coatings. Ideally, designs should avoid trapping
dust and water, encourage movement of air, and avoid open
crevices. Ensuring the metal is accessible for regular
maintenance will also increase longevity.