Metallurgy of Iron

Occurrence
Next to aluminium, iron is the most abundant metal in earth’s crust. Iron is the fourth
most abundant ( about 5 % ) metallic element in the earth’s crust . Because of its
strong
affinity to oxygen, it is not found in nature in the elemental state but only in combined
forms such as oxide. Iron is easily attacked by humid atmosphere. It is generally found
associated with other metals like copper, cobalt and nickel. Principally iron occurs as
oxides, much less as sulphide and sometimes as the carbonate.
The chief sources of iron are –
(i) Red Haematite – Fe2O3, Brown Haematite or Limonite – 2 Fe2O3 . H2O,
Magnetite – Fe3O4
(ii) Siderite – or Spathic Iron ore - FeCO3
(iii) Iron pyrites – FeS2
(iv) Chalcopyrites – CuFeS2

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 Commercial forms of iron
There are three commercial forms of iron .
(i) Cast or Pig iron – It is the most impure form of iron. It contains about 1.5 % to
4.5 % carbon. Other impurities like Si, P, Mn and S are present up to about 1.5 %.
(ii) Wrought or Malleable iron – It is the purest form of iron. It contains about 0.2 %
carbon.
(iii) Steel – It is an alloy of iron with carbon and other elements like manganese,
silicon and phosphorus. It is midway between cast and wrought iron as far as
impurities are concerned. It contains 0.1 to 1.5 % carbon.
The three varieties differ from each other mainly in their carbon content.
The first step in the extraction of iron is the production of pig or cast iron which is
subsequently used in making wrought iron or steel.

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 Extraction of iron
• The extraction of iron is pyrometallurgy. It is the extractive metallurgy which
consists of the thermal treatment given to minerals or ores to recover the
metal. The process involves chemical reactions at elevated temperature.
• The process of extraction of iron is fundamentally very simple as it consists
essentially of the reduction of iron oxide by carbon. But as molten iron
dissolves carbon and other impurities, iron obtained is impure and is known as
pig iron or cast iron. The ore ( red haematite or hydrated oxide or carbonate ) is
calcined in shallow kilns to remove moisture, carbon dioxide etc. The ore
thereby becomes porous and is then more easily reduced in the blast furnace.
• Iron is normally extracted from its oxide ore called haematite and rarely
extracted from carbonate ore called siderite. Iron pyrite is an important source
of sulphur and therefore it is not used in the extraction of iron. The extraction
of iron involves following steps.

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 Manufacture of cast iron
• It is done in following steps.
(i) Washing and concentration or dressing of the ore
Haematite ore is washed with water. It is subjected to magnetic separation. The ore
being magnetic in nature, falls apart as a separate heap. This way the ore becomes
rich in oxide of iron. It is then broken into small pieces of 1” to 2” size, screened
and shifted. This helps to remove gangue. Due to washing, silicious impurities are
removed. The ore is thus concentrated.
(ii) Preliminary roasting and calcinations
The concentrated ore is roasted and calcined with a little coal in shallow kiln
( furnace ) in excess air. Following changes take place during roasting and calcinations.
(i) Moisture escapes as steam and organic matter present burns off to give CO2 and
sulphur and arsenic are oxidized to form their volatile oxides SO2 and As2O3
respectively.
(ii) Ferrous oxide is converted to ferric oxide which avoids formation of ferrous
silicate In the slag during smelting and (iii) The mass becomes porous and thus
makes it more suitable for reduction to metallic iron. Following reactions take
place.
Fe2 O3. 3H2O → Fe2O3 + 3 H2O ↑ ; FeCO3 → FeO + CO2 ↑ ;
• 4 FeO + O2 → 2 Fe2O3
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 (iii) Reduction or smelting in a Blast
Furnace
The roasted and calcined ore ( 8 parts ) is mixed with coke ( 4 parts ) which acts
as a reducing agent and limestone ( 1 part ) which acts as a flux. The mixture is
introduced in a tall Blast Furnace. The blast furnace has two functions (i) to
reduce the ore to metallic iron and (ii) to remove the impurities in the form of
slag.
Description of Blast Furnace
a) It consists of an outer shell which is made of steel plates riveted ( fastened )
together.
From inside it sis lined with fire bricks. ( Refer Figure )
b) It is about 15’ to 120’ tall. ( The height varies from place to place. ) It is 15’ to
24’ in diameter at the wider end near the bottom. ( boshes, lower cone ) It is kept
in a vertical position with the help of iron columns.
c) In its lower part, the furnace gradually narrows down below the boshes. The
lower part of the furnace is called hearth (floor ) or crucible where molten iron
and slag is collected.
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d) The mouth of the furnace i.e. the top is closed by a
double cup and cone arrangement through which
the mixture ( called charge ) of the calcined ore,
limestone and coke is fed from time to time. The
hot gases escape through the flue. ( Refer diagram )
e) The cone is made of iron and is kept tight against
the top of the furnace being counterpoised by
weights

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 Blast Furnace

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• f) A blast of hot and dry air, obtained by hot gases, escaping
from the blast furnace itself and freed from dust in a scrubber ,
is blown into the furnace , just above the hearth by a number of
water-cooled pipes, called tuyeres or twyers ( pipe rings).
• g) Near the bottom of the furnace, there are two outlets on
opposite sides, one for the removal of slag ( called slag hole )
and the other for taking out molten metal ( called metal hole or
tap hole ).
• h) The temperature of the furnace is not constant in all the
parts. It is maximum at the hearth ( about 17000C ) and
decreases slowly towards the throat of the furnace ( about
3000C )
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 The Process
• The charge ( roasted ore + coke + limestone in the
proportion 8: 4:1 ) is introduced in the furnace from the
top. Simultaneously, the furnace is lit and a hot blast of
air is passed through the tuyeres. The different heat
zones of the blast furnace are shown in the figure.
• Reactions in the blast furnace
• Following chemical reactions take place in different
zones of the blast furnace.
• (i) Zone of reduction – ( 3000C to 8000C - i.e. dull red
heat )
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• This is the uppermost zone of the blast furnace. It is called the zone of reduction.
Here the iron oxide from the charge is reduced by carbon monoxide to spongy iron.
Fe2O3 + 3 CO → 2 Fe + 3 CO2 ↑
The reduction of Fe2O3 actually takes place in following three stages.
a) Conversion of ferric oxide to ferroso - ferric oxide
3 Fe2O3 + . CO → CO2 + 2 Fe3O4
b) Conversion of ferroso – ferric oxide to ferrous oxide.
Fe3O4 + CO → CO2 + 3 FeO
c) Conversion of ferrous oxide to metallic iron.
FeO + CO → CO2 + Fe
• When the spongy iron falls in the middle region ( zone of heat absorption ),
limestone, CaCO3 decomposes to give CaO ( lime ) and CO2. Lime thus obtained
acts as a flux. It combines with silica to form a fusible ( meltable ) slag.
• CaCO3 → CaO + CO2 ; CaO + SiO2 → CASiO3 ( slag )
• (ii) Zone of heat absorption – ( 8000C to 12000C – i.e. bright red heat )
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• This is the middle part or zone of the blast furnace.
In this zone, the ascending CO2 is reduced to
carbon monoxide when it reacts with carbon ( coke
).
CO2 + C → 2 CO - 39 kcal
• As the reaction is endothermic, the temperature in
this region falls and comes in the range 8000C –
10000C.

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(iii) Zone of combustion – ( 13000C to 15000C – i.e.
white heat )
This is the zone near the tuyeres . Here the carbon
burns to form CO2 producing tremendous amount
of heat.
C + O2 → CO2 ↑ + 97 kcal
The heat evolved raises the temperature to 15000C.
As the hot gases go up and meet the descending
charge, the temperature falls slowly to about
13000C.
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 (iv) Zone of fusion – (15000C to
19000C )

• In this zone, the spongy iron melts and dissolves

some carbon, phosphorus and silica.
• The molten iron collects at the bottom of the
furnace while the fusible slag floats on it and
protects the iron from oxidation. The layers of
molten iron and slag are withdrawn through
separate tapping holes from time to time.

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• The process is economical as it is continuous one. The
waste gases containing about 25% CO, 15% CO2, 56%
N2 and 4% H2 are let out through the outer pipe. These
are burnt with air to produce heat which is used for
preheating the air blast passed through the tuyeres.
The blast furnace can work day and night for years
together. Iron so obtained is known as Pig Iron. It is
remelted in a vertical furnace ( known as cupola )and
• can be cast or poured into moulds. It is then called cast
iron. Thus cast iron is obtained after remelting pig iron.
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 Varieties of cast iron

• When pig iron in the blast furnace is suddenly cooled,

crystalline cast iron is obtained. It is known as white
cast iron. In this form, carbon is present in the
combined state as iron carbide. It is very hard and
white in colour. On the other hand, if molten iron is
slowly cooled in sand moulds a graphite coloured iron
is formed. It is known as grey cast iron. In this type, a
part of carbon separates out as graphite and gives
grey colour to the metal. It is softer and more coarse
grained than the white form.
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 Products of Blast Furnace
• The products of blast furnace are (i) Pig iron (ii) Slag
(iii) Flue gases .
(i) Pig iron – Average composition of pig iron is : a)
Iron – 92 to 95 % , b) Carbon – 2.5 to 4.5 % c)
Silicon – 0.7 to 3% d) Phosphorus –0.5 to 1 % e)
Manganese - 0.2 to 1 % f) Sulphur – 0.1 to 0.3 %
(ii) Slag - It is mostly calcium silicate containing
some amount of aluminium silicate. It Contains 55
% SiO2 , 30 % CaO and 15 % CO2 and 15 % Al2O3. It
is useful for road making and cement manufacture.

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(iii) Flue gases - The gases leaving the blast furnace
through the flue are known as flue gases. The average
composition of the gaseous mixture is a) CO – 25 % b)
CO2 – 10 % c) N2 – 58 to 60 % d) H2 – 1 to 2 % Due to
the appreciable proportion of carbon monoxide, the
gaseous mixture has a fuel value and hence it is used
for heating the air blast in Cowper’s stoves.
Major part of cast iron is used to manufacture steel. It
is also used for casting metal objects such as pipes,
railings, weights and heavier parts of machinery.
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 Physical and Chemical Properties of
Cast Iron
• (i) Since cast iron is impure, it has melting point ( about 12000C ) lower than that of
pure iron ( about 15300 C).
• (ii) On solidifying, it expands
• (iii) It is harder due to the presence of carbon and silicon.
• (iv) Due to sulphur, it is brittle when red hot ( red short ) and due to phosphorus, it
is brittle when cold ( cold short ).
• (v) It can not be welded and can not be permanently magnetized.
• (vi) Action of air - Pure iron is not affected by dry air. In presence of moist air and
• carbon dioxide, it begins to rust readily forming reddish brown hydrated ferric
oxide. When heated in air, it is oxidized and gets covered with thick bluish black
scales of ferroso – ferric oxide Fe3O4.
• (vii) Action of steam – When steam is passed over iron heated to 8000C to 10000C,
iron is oxidized to Fe3O4.
• 3 Fe + 4 H2O → Fe3O4 + 4 H2 ↑
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