STEEL MAKING PROCESSES

Dr. Laraib Sarfraz Khanzada

Department of Metallurgical Engineering
 The Process route
from ore to steel
Iron ore containing Hot metal
Carbon steel containing
50-70 % Fe containing
Approx. 98.5% Fe
approx 94% Fe

Reduction in blast Oxidation and refining in

furnace with carbon steel furnace
❑ There are as many as two thousand odd
varieties of steels in use. These specifically
differ in their chemical composition. However,
a couple of hundred varieties are
predominantly in use. The chemical
composition of steels broadly divide them into
two major groups, viz. (i) plain carbon steels
and (ii) alloy steels.
❑ The plain carbon steels are essentially alloys of
iron and carbon only whereas, if one or more of
elements other than carbon are added to steel
in significant amounts to ensure specific better
properties such as better mechanical strength,
ductility, electrical and magnetic properties,
corrosion resistance and so on it is known as
an alloy steel.

❑ These specifically added elements are known

as alloying additions in steels.
❑ Steels may contain many other elements such as AI,
Si, Mn, S, P, etc. which are not added specifically for
any specific purpose but are inevitably present
because of their association in the process of iron and
steelmaking and can not be totally eliminated during
the known process of iron and steelmaking. These are
known as impurities in steel.

❑ Every attempt is made to minimise them during the

process of steelmaking but such efforts are costly and
special tech-niques are required for decreasing their
contents below a certain level in the case of each
element.
❑ For cheaper variety of steels therefore their contents at
high levels are tolerated. These high. levels are
however such that the properties of steels are not
signifi-cantly adversely affected. These tolerable limits
of impurities are considered as 'safe limits' and the
impurity levels are maintained below these safe limits.

❑ For example, for ordinary steels sulphur contents up

to 0.05% are tolerable ,whereas for several special
steels the limit goes on decreasing to as low as
0.005% or even lower. For most high quality steels
now the total impurity level acceptable is below 100
ppm and the aim is 45 ppm.
Plain carbon steels are broadly sub-divided into four
major types based on their carbon contents. These are
not strict divisions based on carbon contents but are
generally broad divisions as a basis of classification.
This division is definitely useful. These are:

(i) Soft or low carbon steels up to 0·15% C

(ii) Mild steels in the range 0·15-0·35% C
(iii) Medium carbon steels in the range 0·35-0·65% C
(iv) High carbon steels in the range 0·65-1·75% C
The alloy steels are broadly sub-divided into three groups
on the basis of the total alloying elements present. This
division is also only a broad division and not a rigid one.
This is :

(i) Low alloy steels up to 5% total alloying contents

(ii) Medium alloy steels 5-10% total alloying
(iii) High alloy steels above 10% total alloying
 [F e] + [O] = (FeO)

[C] + [O] = {CO}

[S i] + 2 [ 0 ] = (Si 0 2)
[Mn]+ [0] =(M n O) I

2[P]+ 5 [ 0 ] =(P2 0 5)
[s] + (Cao) = (CaS) + [O]
The products in the aforementioned reactions are only those which
are stable at steelmaking temperatures. The oxides which are not
thermodynamically stable at steelmaking temperatures need not be
considered here.
Except the sulphur reaction all the rest are oxidation processes

and are favoured under the oxidizing condition of steelmaking.

In the case of oxidation of carbon the product, being a gas, passes
off into the atmosphere but the rest of the oxide products shall
remain in contact with the iron melt in the form of a slag phase.
❑ In steelmaking the reactions should move to the right in
preference to the oxidation of iron and that the danger of
reversion of an impurity to the metal phase is as remote as
possible.

❑ From the point of view of law of mass action the required

conditions can be achieved by increasing the activities of the
reactants and decreasing those of the products.

❑ For a given composition of iron melt the activity of the impurity is

fixed and hence can not be increased.

❑ The oxidising potential of an oxidising agent can be increased.

• The oxidising potential of an oxidising agent can be increased by using
atmospheric air (ao = 0·21) in place of iron oxide in slag phase and pure
oxygen (ao = 1) in place of air. But once the nature of the oxidizing agent
is chosen it cannot be increased.
• The activity of the product can however be decreased by combining it
with oxide of opposite chemical character, i.e. an acid oxide product is
mixed with basic oxide and vice-versa.
• As far as the physical requirement of the oxide product is concerned
it should be readily separable from the iron melt.
• This is achieved by keeping the slag and the metal both as thin liquids
so that the metal being heavier settles down and the slag floats on top in
the form of two immiscible liquids which can be separated readily.
If the oxide products of iron refining reactions are examined, silicon and
phosphorus form acid oxides and hence a basic flux is needed to form a
suitable slag for their effective removal.

The higher the proportion of base available the lesser will be the danger of
backward reaction. For manganese elimination, since manganese oxide is
basic, an acid flux will be required. The nature of the process itself has
made the task little simpler.

During refining, being the largest bulk, iron itself gets oxidised to some
extent as (FeO) which is basic in nature. It is possible to adjust the
contents of silicon and manganese in pig iron such that the amounts of
(FeO + MnO) formed during refining would be able to form a slag
essentially of the type FeOMnOSi02 and fix up silica in it.
❑In such a slag P20S is not stable because (FeO + MnO) together
are not strong enough bases to fix it up in slag.

❑In order to oxidise phosphorus in preference to iron, a strong

external base like CaO and/or MgO is needed in sufficient
proportion to form a basic slag to hold P20S without any danger of
its reversion.

❑Phosphorus is best eliminated by a slag of the type CaOFeO P205

It is quite interesting to note that such a slag is also capable of
removing sulphur from iron melt to a certain extent.
 The steelmaking processes can now be divided into two broad
categories :

(i)when silicon is the chief impurity to be eliminated from iron and that
phosphorus and sulphur need not be eliminated and,

(ii)when phosphorus and, to some extent, ,sulphur are the chief impurities to be
eliminated along with even silicon.
The elimination of manganese will take place under both the categories. In

the finished steel, except a few exceptions, phosphorus and sulphur

each must be below 0·05%. If phosphorus is above this limit, steel becomes
coldshort and if sulphur is more it becomes hotshort. Higher sulphur contents
are recommended for freecutting variety of steels and a slightly high
phosphorus level is desirable for efficient pack rolling of steel sheets.
❑ If the pig iron composition is such that phosphorus and sulphur both are
below 0·05% and, therefore, need not be eliminated it is possible to
remove silicon along with manganese in such a way that slag of the type
MnOFeOSi02 is formed without the necessity of addition of an external flux.
Such a process of steelmaking is called acid steelmaking process which is
carried out in an acid brick lined furnace.

❑ On the other hand, to eliminate phosphorus and sulphur, the reverse

reaction rate can only be suppressed if the slag contains a good amount of
stronger base than as is internally available in the form of FeO and MnO.
External CaO (and also MgO) is used as a flux and slag of the type CaO-
FeOP205 is made. Such a process is called basic steelmaking process. The
furnace lining in this case has to be basic in nature.
❑ In brief the composition of pig iron is the only factor that determines
the acid or the basic character of the process to be adopted for
steelmaking. In an acid process slag is acidic and the furnace lining
has to be acidic to withstand the slag.

❑ Similarly in a basic process the slag contains excess basic oxide and
the furnace lining should be basic in nature. If the lining is of opposite
chemical character slag will readily react with the lining and cause
damage to the furnace. Besides the acid or the basic nature, the slag
needs to possess many other physical and chemical properties to
carry out refining efficiently.
• The slag comprising of simple and/or complex
compounds consists of solutions of oxides from
gangue minerals, sulphides from the charge or fuel
and in some cases halides added as flux.
• Slag cover protects the metal and from oxidation and
prevents heat losses due to its poor thermal
conductivity.

• It protects the melt from contamination from the

furnace atmosphere and from the combustion products
of the fuel
• In primary extraction, slags accept gangue and
unreduced oxides, whereas in refining they act as
reservoir of chemical reactant(s) and absorber of
extracted impurities.
In order to achieve these objectives, slag must possess
certain optimum level of physical properties:
❖ Low melting point,
❖ Low viscosity,
❖ Low surface tension,
❖ High diffusivity
and chemical Properties:
❖ Basicity,
❖ Oxidation potential and
❖ Thermodynamic properties
The required properties of slags are controlled by the
composition and structure.
❑ There are two principal types of bonds found in
crystals: electrovalent and covalent.

❑ Electrovalent bond strength is lower than the covalent

bond. High temperature is required to destroy the
covalent bond.

❑ However, oxides exhibit varying proportion of both ionic

and covalent bonding in slag.

❑ Ionic bond fraction indicates the tendency to

dissociate in liquid state.
Relative dimensions of cations and anions and type of bonds
between them are important factors in controlling the structure of
pure oxides
 TiO2, SiO2 and P2O5, bonding is mainly covalent and the
electrovalent proportion is strong due to small cations
carrying higher charge with a coordination number of 4.

These simple ions combine to form complex anions

such as SiO4-4 and PO3-4leading to the formation of stable
hexagonal network in slag systems.
Hence they are classified as ‘network formers’ or
“acidic oxides”. For example
SiO2 + 2O2- = SiO4-4
P2O5 + 3O2- =2(PO3-4)
The oxides with high ionic fraction form simple ions
on heating beyond the melting point or when
incorporated into a liquid silicate slag. For example :
CaO→Ca2+ + O2-
Na2O → 2Na+ + O2-

As they destroy the hexagonal network of silica by

breaking the bond they are called ‘network
breakers’or‘basic oxides.
Oxide z/(Rc+Ra) Ionic
Coordination Nature of the
fraction
number Oxide
of bond
Na2O 0.18 0.65 Solid- -Liquid
6 6 to 8
BaO 0.27 0.65 8 8 to 12
SrO 0.32 0.61 8 Network breakers

CaO 0.35 0.61 6 or

MnO 0.42 0.47 6 6 to 8 Basic oxides

FeO 0.44 0.38 6 6
Oxides like Fe2O3, Cr2O3 and
ZnO 0.44 0.44 6
Al2O3 are known to be
Mgo 0.48 0.54 6
amphoteric due to their dual
BeO 0.69 0.44 4
characteristics because they
…………. ……………... ……………... …… ……... …………………...
Cr2O3 0.72 0.41 4
behave like acids in basic slag
and as bases in acidic slag.
Fe2O3 0.75 0.36 4 Amphoteric oxides

Al2O3 0.83 0.44 6 4 to 6

…………. ……………... …………….. …….. ………. …………………...

TiO2 0.93 0.41 4 Network formers

SiO2 1.22 0.36 4 4 or

P2O5 1.66 0.28 4 4 Acidic oxides
It is well known that most of the slags are silicates. When a basic
oxide is incorporated in to the hexagonal network of silica it forms
two simple ions.
The fraction of basic oxide, expressed as O/Si ratio plays an
important role in destroying the number of Si-O joints.
O/Si Formula Structure

2/1 Si O2 Silica tetrahedra form a perfect three

dimensional hexagonal network
5/2 MO.2 One vertex joint in each tetrahedron
SiO2 breaks to produce two-dimensional
lamellar structure.
3/1 MO. Si O2 Two vertex joints in each tetrahedron
break to produce a fibrous structure
7/2 3MO. Three vertex joints in each tetrahedron
2SiO2 break
4/1 2MO.SiO2 All the four joints break
 Thank You