Smarajit Sarkar

Department of Metallurgical and Materials Engineering

NIT Rourkela

Ahindra Ghosh and Amit Chatterjee: Ironmaking and Steelmaking Theory and Practice, PrenticeHall of India Private Limited, 2008
Anil K. Biswas: Principles of Blast Furnace Ironmaking, SBA Publication,1999
R.H.Tupkary and V.R.Tupkary: An Introduction to Modern Iron Making, Khanna Publishers.
R.H.Tupkary and V.R.Tupkary: An Introduction to Modern Steel Making, Khanna Publishers.
David H. Wakelin (ed.): The Making, Shaping and Treating of Steel (Ironmaking Volume), The
AISE Steel Foundation, 2004.
Richard J.Fruehan (ed.): The Making, Shaping and Treating of Steel (Steeelmaking Volume), The
AISE Steel Foundation, 2004.
A.Ghosh, Secondary Steel Making Principle & Applications, CRC Press 2001.
R.G.Ward: Physical Chemistry of iron & steel making, ELBS and Edward Arnold, 1962.
F.P.Edneral: Electrometallurgy of Steel and Ferro-Alloys, Vol.1 Mir Publishers,1979
B. Ozturk and R. J. Fruehan,: "Kinetics of the Reaction of SiO(g) with Carbon Saturated Iron":
Metall. Trans. B, Vol. 16B, 1985, p. 121.
B. Ozturk and R. J. Fruehan: "The Reaction of SiO(g) with Liquid Slags, Metall. Trans.B,
Volume 17B, 1986, p. 397.
B. Ozturk and R. J. Fruehan:.Transfer of Silicon in Blast Furnace": , Proceedings of the fifth
International Iron and Steel Congress, Washington D.C., 1986, p. 959.
P. F. Nogueira and R. J. Fruehan: Blast Furnace Softening and Melting Phenomena - Melting
Onset in Acid and Basic Pellets", , ISS-AIME lronmaking Conference, 2002, pp. 585.

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 techniques 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 significantly
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
(ii) Mild steels
(iii) Medium carbon steels
(iv) High carbon steels

up to 015% C
in the range 015-035% C
in the range 035-065% C
in the range 065-175% 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

The

products in the above 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 = 021) 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 FeO-MnO-Si02 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 CaO-FeO-P 205 It

is quite interesting to note that such a slag is also capableof
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 005%. If phosphorus is above this limit, steel becomes coldshort and if sulphur is more it becomes hot-short. Higher sulphur contents
are recommended for free-cutting 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 005% and, therefore, need not be eliminated it is possible to
remove silicon along with manganese in such a way that slag of the type
MnO-FeO-Si02 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-FeO-P205 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.

By
Dr. Smarajit Sarkar
Associate Professor
Dept. of Metallurgical and Materials
Engg.
National institute of Technology,
Rourkela

Introduction to metallurgical slag

Structure of pure oxide
Role of ionic radii
Metal oxygen bond
Structure of slag
Properties of slag
Basicity
Oxidising power
Sulphide capacity
Electrical and thermal conductivity
Viscosity
Surface tension
Constitution of slag

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 PO3-4 leading 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 :
CaOCa2+ + O2Na2O 2Na+ + O2-

As they destroy the hexagonal network of

silica by breaking the bond they are called
network breakersorbasic oxides.

Oxide

z/(Rc+Ra)

Ionic

Coordination

Nature of the

fraction

number

Oxide

of bond
Solid- -Liquid
Na2O

0.18

0.65

6 to 8

BaO

0.27

0.65

8 to 12

SrO

0.32

0.61

Network
breakers

CaO

0.35

0.61

MnO

0.42

0.47

6 to 8

FeO

0.44

0.38

ZnO

0.44

0.44

Mgo

0.48

0.54

BeO

0.69

0.44

. ... ...
Cr2O3

0.72

0.41

Fe2O3

0.75

0.36

or

...

Basic oxides

...

Amphoteric
oxides

Al2O3

0.83

4 to 6

. ... ..

..

TiO2

Network

0.93

0.44

0.41

...

SiO2

1.22

0.36

formers
or

P2O5

1.66

0.28

Acidic oxides

Oxides like Fe2O3, Cr2O3 and

Al2O3 are known to be
amphoteric due to their dual
characteristics because they
behave like acids in basic
slag
and as bases in acidic slag.

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
2/1
5/2
3/1

7/2
4/1

Formula Structure
Si O2
Silica tetrahedra form a perfect
three dimensional hexagonal
network
MO.2
One vertex joint in each tetrahedron
SiO2
breaks to produce two-dimensional
lamellar structure.
MO. Si O2 Two vertex joints in each
tetrahedron break to produce a
fibrous structure
3MO.
Three vertex joints in each
2SiO2
tetrahedron break
2MO.SiO2 All the four joints break

A knowledge of various chemical and

physical
properties of slag is essential in order to
adjust them according to the need of
extraction and refining processes.
1. Basicity of Slags
In slag systems, a basic oxide generates O2anion while an acidic oxide forms a complex
by accepting one or more O2 anions:
Base acid + O2-

For example, SiO2, P2O5, CO2, SO3 etc are acidic oxides
because they accept O2- anions as per the reaction:
(SiO2) + 2 (O2-) = SiO44On the other hand basic oxides like CaO, Na2O, MnO etc.
generate O2- anions:
(CaO) Ca2+ +O2The amphoteric oxides like Al2O3, Cr2O3 Fe2O3 behave as
bases in the presence of acid (s) or as acids in presence of
base (s):
(Al2O3) + (O2-) = 2 (Al O2-) or (Al2 O4 2- )
(Al2O3) = 2(Al3+) + 3(O2-)

In a binary slag viz. CaO-SiO2 the basicity

index (I) is given as:
I = wt % CaO / wt % SiO2
For example a complex slag consisting of
CaO, MgO, SiO2 and P2O5 employed in
dephosphorisation of steel, basicity index2 is
estimated as follows:

I=

wt%CaO + 2 3 wt%MgO
wt%SiO 2 + wt%P2 O 5

Oxidizing power means the ability of the

slag to take part in smooth transfer of
oxygen from and to the metallic bath.
The oxidizing power of the slag depends
on the activity of the iron oxide present in
the slag.
The equilibrium between iron oxide in slag
and oxygen dissolved in metal is
represented as:

(FeO) = [ Fe ] + [ O ]
[ a Fe ][ a O ] Thus a O a FeO
K=

(a )
FeO

Since slags are employed to remove sulphur

from metal, chemistry of sulphur in silicate
slags becomes interesting.
Sulphide is soluble in silicate melts but
elemental sulphur does not dissolve to any
appreciable extent.

1
1
S 2 ( g ) (O 2 ) O2 ( g ) ( S 2 )
2
2

a
K
a
S 2

p O2

O2

pH2

S 2

.
O 2

S 2

(18)

p O2

pS
2

(19)

The sulphur affinity of a slag, presented as molar

sulphide capacity is defined by the equation:
C S x

S 2

p O2

pS

O 2

S 2

(20)

or a more useful term wt % sulphide capacity5 for

technologist is defined as
1

p O2

C S (wt% S)

pS

(21)

Thus under similar conditions a slag with a high

Cs will definitely hold sulphur more strongly than
the other with a low Cs and hence will prove to be
a better desulphuriser in a metallurgical process.

Molten silica is a poor electrical conductor3. However

its conductivity increases to a great extent by addition
of basic oxides e.g. CaO, FeO or MnO as flux.
This increase is due to the formation of ions.
The conductivity values serve as a measure of degree
of ionization of the slag. The electrical conductivity of
slags depends on the number of ions present and the
viscosity of liquid slag in which they are present.
Thus conductivity will be greater in liquid state and
further increases with the temperature.
In general thermal conductivity of slag is very low but
heat losses are much higher due to convection.

Viscosity of slags are controlled by composition

and temperature. The viscosity , of a slag of a
given composition decreases exponentially with
increase of temperature according to the
Arrhenius equation:
= A exp (E / RT)

Basic oxides or halides with large ionic bond

fraction are more effective in reducing viscosity
than those with smaller bond fraction by
breaking bonds between the silica tetrahedra.

Effect of addition of flux on activation

energy

Viscosity decreases rapidly with temperature for both basic

as well as acid slags.
But basic slags with higher melting points are more
sensitive to temperature.
This indicates that activation energy for viscous flow of
basic slags is much lower than for acid slags.

Use of CaF2 as flux is more effective in reducing viscosity of

basic slags than that of acidic slags.
This may be due to ability of F- ions to break the hexagonal
network of silica and the low melting point of undissociated
CaF2.

Figure shows that addition of Al2O3 to a

basic slag increases viscosity by acting
as network former.
Addition of Al2O3 to an acidic slag
reduces viscosity because it now acts
as network breaker.

The high rates of reaction in basic oxygen

converters is due to the physical conditions of the
metal, slag and gaseous phases in the converter.

The theories regarding rapid reaction rates rely

heavily on the formation of slag metal emulsion
and slag foams leading to creation of the large
required reaction surface.

The most important feature of emulsion and foam

is the considerable increase of the interfacial area
between the two phases leading to the high rate of
reaction.

As surface tension is the work required to create

unit area of the new surface, the necessary
energy for emulsifying a liquid or a gas in
another liquid increases with increasing surface
tension value.

In a similar manner energy is liberated when

interfacial area decreases.

Hence a low interfacial tension favors both

formation and retention of emulsion.

On this basis slag / metal and slag /gas systems are

not suitable for emulsification because of the high
equilibrium slag/metal interfacial tension.

However the slag/metal interfacial tension is

considerably lowered to 1/100 of the equilibrium
value due to mass transfer.

Addition of SiO2 or P2O5 to a basic oxide lowers3 the

surface tension due to the absorption of a thin layer
of anions, viz. SiO44- , PO43- on the surface.

It has been reported that lowering of surface tension

of FeO by excess oxygen.

The major constituents

of iron blast furnace
slags can be
represented by a
ternary system: SiO2
CaO Al2O3.

On the other hand all

the steelmaking and
many nonferrous slags
are represented by the
ternary system: SiO2CaO FeO.

1.Basic open hearth steel furnace

2.Acid open hearth steel furnace
3.Basic oxygen converter
4.Copper reverberatory
5.Copper oxide blast furnace
6.Lead blast furnace
7.Tin smelting

As surface tension is the work required to create

unit area of the new surface, the necessary
energy for emulsifying a liquid or a gas in
another liquid increases with increasing surface
tension value.

In a similar manner energy is liberated when

interfacial area decreases.

Hence a low interfacial tension favors both

formation and retention of emulsion.

On this basis slag / metal and slag /gas systems are

not suitable for emulsification because of the high
equilibrium slag/metal interfacial tension.

However the slag/metal interfacial tension is

considerably lowered to 1/100 of the equilibrium
value due to mass transfer.

Addition of SiO2 or P2O5 to a basic oxide lowers3 the

surface tension due to the absorption of a thin layer
of anions, viz. SiO44- , PO43- on the surface.

It has been reported that lowering of surface tension

of FeO by excess oxygen.

The major constituents

of iron blast furnace
slags can be
represented by a
ternary system: SiO2
CaO Al2O3.

On the other hand all

the steelmaking and
many nonferrous slags
are represented by the
ternary system: SiO2CaO FeO.

1.Basic open hearth steel furnace

2.Acid open hearth steel furnace
3.Basic oxygen converter
4.Copper reverberatory
5.Copper oxide blast furnace
6.Lead blast furnace
7.Tin smelting

Introduction

Changing Pattern of Steel Making

Modern steel making BOF / LD steel

making

Silicon Reaction

Manganese reaction

Phosphorous Reaction

Carbon Reaction

Vacuum Degassing

Steelmaking is conversion of pig iron containing about

10 wt weight of carbon , silicon, manganese,
phosphorus, sulphur etc to steel with a controlled
amount of impurities to the extent of about 1 weight
percent.

With the exception of sulphur removal of all other

impurities is favored under oxidizing conditions.

In the case of oxidation of carbon the product, being a

gas, passes off into the atmosphere but rest of the oxide
products shall remain in contact with the iron melt in the
form of a slag phase.

SiO2, MnO and P2O5 formed by oxidation of Si, Mn and

P, respectively will join the slag phase.

The formation of these oxides can be facilitated by

decreasing their activities which is possible by providing
oxides of opposite chemical character serving as flux.

As SiO2 and P2O5 are acid oxides a basic flux is required

for formation and easy removal of the slag.

A strong basic slag is formed by addition of CaO and / or

MgO to absorb P2O5 and SiO2.

The removal of carbon will take place in the form of

gaseous products (CO).

During refining, controlled oxidation of the impurities in hot metal

(with the exception of sulphur) takes place once oxygen is blown at
supersonic speeds onto the liquid bath.

The interaction of the oxygen jet(s) with the bath produces crater(s)
on the surface, from the outer lip(s) of which, a large number of tiny
metal droplets get splashed.

These droplets reside for a short time in the slag above the bath.
Therefore, the existence of a metal-slag-gas emulsion within the
vessel, virtually during the entire blowing/refining period is an integral
part of BOF steelmaking.

This is the reason why the slag-metal reactions like

dephosphorisation and gas-metal reactions like decarburisation
proceed so rapidly in the BOF process

The droplets ultimately return to the metal bath. The extent of

emulsification varies at different stages of the blowing period, as
depicted schematically .

A minimum amount of slag, with the desired characteristics, is

necessary for ensuring that the emulsion is stable, i.e. the slag
should not be too viscous, or too 'watery'. Only in this way can the
kinetics of the removal of the impurities be enhanced.

For encouraging quick formation of the appropriate type of slag,

lime/dolomite/other fluxing agents with adequate reactivity are added right from
the beginning of the blow. The reactivity of the fluxing agents, primarily lime
(consumption 60-100 kg/tls), determines how quickly slag is formed (typically
within 4-5 minutes after the commencement of the blow).

The rate at which oxygen is blown through the lance, the number of openings
(holes) on the lance tip, the distance between the lance tip and the bath surface
(lance height), the characteristics of the oxygen jets as they impinge on the bath
surface, the volume, basicity and fluidity of the slag, the temperature conditions
in the bath and many other operational variables influence the refining.

There are two distinct zones of refining in a LD vessel viz. the

reactions in the emulsion and in the bulk phase. The
contribution of bulk refining, i.e. refining in impact zone and at
the bulk slag-metal interface, is dominant in the beginning
since emulsion is yet to form properly. It has also been
believed that substantial decarburisation of droplets can occur
because of its free exposure to an oxidising gas, particularly
in the beginning. As the emulsion builds up the emulsion
refining attains a dominant role. The bulk phase refining
dominates again towards the end when the emulsion
collapses.

Conditions for dephosphorisation are that the slag should be basic, thin and
oxidising and, that the temperature should be low.

Dephosphorisation, therefore, does not take place efficiently until such a slag is
formed. Such a slag is formed in LD process only after the initial 4-6 minutes of
blowing.

The rate of dephosphorisation picks up concurrently with the rate of

decarburisation.

For efficient decarburisation as well as dephosphorisation the slag should,

therefore, form as early as possible in the process. If a preformed slag is
present as in a double slag practice wherein the second, slag is retained in the
vessel in part or full, the decarburisation rate curve rises more steeply in the
beginning

Dephosphorisation is very rapid in the emulsion because of

the increased interfacial area and efficient mass transport.
Phosphorus should, therefore, be fully eliminated before the
emulsion collapses. If this is not achieved the heat will have
to be kept waiting for dephosphorisation to take place and, in
the bulk phase, it is extremely slow as compared to that in the
emulsion. In general dephosphorisation should be over by the
time carbon is down to 07-10%, i.e. well ahead of the
collapse of emulsion which begins at around 03%C.

The relative rates of dephosphorisation and decarburisation can be

controlled by adjusting the lance height or by adjusting the flow rate of
oxygen.

Raising the height of the lance or decreasing the oxygen pressure

decreases the gas-metal reactions in the emulsion (i.e. decarburisation)
and vice versa.

The dephosphorisation reaction is thus relatively increased by the above

change and vice versa. Towards the end when temperature is high the
danger of phosphorus reversion does exist but it can be prevented by
maintaining a high basicity of the slag.

The process of decarburization includes at least three stages:

supply of reagents - carbon and oxygen - to the reaction site;

the reaction [c] + [0] proper; and

evolution of reaction products - CO bubbles into the gaseous

phase .

. The apparent activation energy of the reaction [C] + [0] = CO is

relatively small (according to various researchers, E = 80000120000 J/mol), which suggests that the reaction occurs practically
instantaneously. The solubility of CO in molten steel is also
negligible. Accordingly, the process can be limited by either the first
or the third stage.

The nature of kinetic curves of carbon burning-off at its various

concentrations is different: on attaining a certain 'critical level of
concentration of carbon (0.15-0.35%), the rate of carbon oxidation is
observed to drop noticeably.

It has also been established in experiments that the critical carbon

concentration is determined by the intensity of supply of oxidant to the bath
(it increases with increasing intensity of oxygen supply and decreases
during bath boil or metal stirring).

Thus, at carbon concentrations above the critical value, the intensity of

decarburisation reaction is determined by the supply of the oxidant and at
those below the critical value, by carbon diffusion to the reaction place .

This means practically that, if the carbon content of the metal is sufficiently
high, the rate of carbon oxidation will be higher at a higher intensity of oxygen
supply. At low concentrations of carbon, however, a higher level of intensity of
oxygen supply will not produce the desired effect and the bath should be
agitated forcedly (in order to intensify the supply of carbon to the reaction
place) so as to increase the rate of carbon oxidation.

The rate of decarburization can also be limited by the third stage, the evolution of CO.
For a bubble of CO to form in metal, It must overcome the pressure of the column of
metal (pm), slag (psl), and of the atmosphere (pat) above the bubble and also the forces
of the cohesion with the liquid, 2/r i.e.
pCOev pm + psl + pat + 2/r

The value of 2/r becomes practically sensible at low values of bubble radius: at r > I
mm it can be neglected. Formation of bubbles in the bulk of liquid metal is practically
impossible.. They can only form on interfaces between. phases, such as slag - metal,
non-metallic inclusion - metal, gas bubble - metal or lining - metal. The most favorable
conditions for the nucleation of CO bubbles exist on boundaries between the metal
and refractory lining which has a rough surface and is poorly wettable by the metal

Slag evolution
During Blow

High silicon pig iron is required in the acid

steelmaking processes to make relatively acid slag
to ensure longer life of the refractory lining.

Oxidation of silicon also generates sufficient heat

required in case of the Bessemer process.

However basic steelmaking processes need low

silicon iron because the entire amount of acid silica
due to the oxidation of silicon has to be neutralized
by lime to produce slag with basicity (CaO / SiO 2
ratio) between 2 and 4 needed for effective
desulphurisation and dephosphorisation.

Due to the strong attraction between iron and silicon,

the Fe-Si system exhibits large negative deviation
from the Raoults low. The activity coefficient of silicon
in iron in presence of other elements is given by :

log fSi = 0.18%C + 0.11% Si + 0.058% Al

-0.058 %S + 0.025 % V + 0.014 % Cu
+ 0.005 % Ni
+ 0.002 % Mn 0.0023 % Co 0. 23 %O

Oxidation of silicon is an exothermic reaction and

provides some of the heat necessary for rise of
temperature of the bath during blowing.

Si O reaction is governed by G0 vs T equation:

[Si ]+ 2 [O] = (SiO2 ), Go = -14200 + 55.0 T cals.

The activity coefficient of oxygen decreases and

that of silicon increases with increasing silicon
content in iron.

Silica is a very stable oxide, hence once silicon is

oxidised to SiO2 the danger of its reversion does
not arise.

a SiO 2

a Si aO

% Si % O
2

a SiO 2

f Si .% Si f O .% O
a SiO 2
f Si f O2 . K

( 20 )

a SiO 2

2.8 10 5

Si

f O2

( 21)

The extremely low activity of silica in basic steelmaking slag poses

no danger of preferential reduction of silica like that of phosphorus
removal.

In basic steelmaking process the silicon content of pig iron should

be kept as low as possible to decrease the lime consumption with
the prime objective of controlling the required basicity for
phosphorus removal at a minimum slag volume.

In case of high silicon entering the basic steelmaking furnace

double slag practice has to be adopted.

Alternatively, external desiliconisation of the hot metal has to be

done outside the blast furnace before charging it in a basic
steelmaking furnace.

About 50 to 75% of the manganese in the

burden gets reduced along with the pig iron
resulting its manganese content between 0.5
to 2.5%.
During steelmaking major amount of
manganese is lost into the slag and very little
is utilized to meet the specifications.
Some manganese is required to control the
deleterious effects of sulphur and oxygen and
also for improvement of mechanical
properties of the steel.

Hence conditions for maximum recovery of

manganese can be derived by considering the
equilibria:
(Fe2+) + [Mn] = (Mn2+) +[Fe]
K
or K

( a Mn 2 ) a Fe
( a Fe 2 ) a Mn

( Mn 2 ) f Fe % Fe

(FeO) +[ Mn] = (MnO) + [Fe]

( Fe 2 ) f Mn % Mn

( 23)

( Mn 2 ) % Fe

( 24 )

( Fe 2 ) % Mn

equilibrium
( At
)
( Fe 2 ) the Mn slag-metal distribution
Mn 2
K is given by
relation
% Mn
% Fe

( 25)

From the equation it is apparent that the

conditions for the highest possible recovery of Mn
i.e. minimum slag-metal distribution ratio are
i) min (Fe2+), requiring a low FeO content in the
slag.
ii) min K requires a low SiO2 content and a high
temperature as evident from the relation showing
effect various anions in the slag.

log K 3.1 SiO 4 2.5 PO 3 2.4 O 2 1.5 F

4

( 26 )

From the figure it is

evident that for slags
containing about 20%
MnO, a maximum of 0.1%
Mn is found in metal.
The slag containing 50%
SiO2 (the rest being FeO
and MnO), with increasing
Mn content of the metal
the (MnO) content of the
slag increases whereas
the oxygen content of the
metal decreases and
silicon content increases.

Despite its very low boiling point significant

amount of P gets dissolved in pig iron due to
strong attraction for iron.
Making use of the interaction coefficients for the
effect of various elements on the activity
coefficient of phosphorus in iron, the activity of P
can be estimated by the expression:
logfP = 0.13%C + 0.13%O + 0.12%Si + 0.062
%P + 0.024%Cu + 0.028%S + 0.006%Mn
0.0002%Ni 0.03%Cr

A very close stability of FeO, Fe2O3 and P2O5 is evident

from the iron and phosphorus lines in the Ellingham
diagram.
Hence practically all the phosphorus present in the ore
gets reduced along with iron in the blast furnace and
joins pig iron.
During steelmaking the activity of P2O5 in the slag of
basicity 2.4 is reduced drastically to 10-15-10-20.
Activity of P2O5 in steelmakig slag is very low even if it
contains 25% P2O5.

i.e. 2[P] + 5[O] + 3(O2-) = 2 (PO43-)

(12)

Thus for effective removal of phosphorus basic steelmaking

processes have to employ slags of high basicity.
The distribution of phosphorus between slag and metal can
be dessribed as
2[P] + 5(FeO) + 3 (CaO) = (3 CaO.P2O5) + 5[Fe]
i.e. 2[P] + 5[O] + 3(O2-) = 2 (PO43-)

2
a PO
3
4

a2P .a5O .a (3O 2 )

Applying Temkin rule :

2
PO
3

(14 )

f P % P fO % O
2

(13)

3
O 2

The dephosphorising index, D P which is the ratio of phosphorus in slag to that in metal, is given as
DP

( PO 3 )
4

% P

1/ 2

%O5/ 2 ( O

)3/ 2

(15)

From the figure it is clear that DP

increases with increase in the
(FeO) content upto 15% due to
the high oxidizing power.
Beyond this DP decreases due to
decrease in the lime proportion.

Dephosphorisation is more
effective at lower temperature
because DP increases with
decrease of temperature.

The soda ash is 100 times more effective compared to lime

on molar basis but it is avoided in practice due to its severe
corrosive action on furnace lining.
The magnesia content of a basic steelmaking slag reaches
equilibrium with the lining hence not under control and MnO
depends on charge and hence not much adjustable.
The steel maker has the option of controlling lime, silica and
FeO.
For charges containing high % P more than one slags are
made to dephosphorise metal bath to the desired level.
In brief ,high basicity, low temperature, and FeO content
around 15% favour dephosphorisation of metal by basic
slags.

The optimum conditions for dephosphorisation can be

derived from the equation defining the index:
DP

( PO 3 )
4

% P

1/ 2

%O5/ 2 (O

)3/ 2

Basic slag gives a high value of O22. High lime content lime is the divalent oxide making the
largest contribution to K (log K' = 21N'Ca++ + 18 N'Mg++ +
13N'Mn++ + 12 N'Fe++
3. Ferrous oxide close to 15% .
4. Low temperature gives a high value of K.
1.

In refining of steel oxidation of Si, Mn and P takes

place at the slag-metal interface.

The oxidation of carbon practically does not take place

at the slag-metal interface because of the difficulty of
nucleation of CO bubbles there.

C-O reaction takes place at the gas metal interface

since it eliminates the necessity of nucleating gas
bubbles.

During refining of steel oxygen has to dissolve first in

the bath before it reacts with the dissolved impurities.

In the absence of other slag forming constituents at

1600oC liquid iron can dissolve oxygen up to at 0.23
wt.%

In steel making the reaction between carbon

and dissolved oxygen is of utmost importance.

Generally pig iron contains about 4 wt%

carbon.

The solubility of carbon in steel is effected by

the presence of impurities and alloying
elements.

Presence of Nb, V, Cr, Mn and W increase

solubility of carbon in iron where as presence
of Co, Ni, Sn and Cu decrease it.

Thus solubility of carbon in steel can be calculated by combining the binary data from the following equation:

Oxidation of Carbon can be discussed

according to the reaction:
C + O = CO,
G0= -5350 9.48T cals.

pCO
pCO
K

a c aO [ fc%C ][ fo%O]

pCO
pCO
[% C ][% O ]

K fc fo
K
At any chosen pressure of CO, % C vs % O
indicates inverse hyperbolic relationship

During oxidation period oxygen is continuously transferred

from the slag to the bath, where it continuously reacts with
carbon to give CO.
The main resistance to the oxygen flow is the slagmetal and
the metalgas interfaces, whereas inside the steel bath the
transfer of dissolved oxygen is very fast.

The activity coefficient

of carbon in iron
increases with
increasing carbon
content and that of
oxygen decreases with
increasing carbon
content.
The net result is that the
product [% C] [% O] for
a given pCO decreases
slightly with increasing
carbon content as
shown in Figure

Since steel making is a dynamic process, the

concentration of carbon and oxygen in the bulk
metal phase is not in equilibrium with the
prevailing CO-pressure in the bubbles.

At the gas bubblemetal interface the reaction is

close to equilibrium.

The experimentally observed excess oxygen and

carbon in the bulk metal phase is thus helpful in
transfer of the reactants by diffusion to the gasmetal interface in the violently stirred metal bath.

As [% O] increases with (aFeO) in slag and [% O]

decreases with [% C] in the bath.

it follows that the iron oxide contents of the slag

increases with decreasing carbon in steel during
refining.

Hence there is a general trend in the variation of slag

composition with the carbon content of the metal.

For a given total iron oxide in a slag, a lower carbon

in the steel corresponds to a higher sum of (% SiO 2 +
% P2O5) in the slag.

Within the range of basic slags, for a given sum of %

CaO + % MgO + % MnO the carbon content of steel
does not vary much with the FeO content of the slag.

During steelmaking i.e. refining of pig iron where

impurities like carbon, silicon, manganese and
phosphorus are eliminated to the required level
oxygen, nitrogen and hydrogen get dissolved as
harmful impurities.

As solubility decreases with decrease of temperature

excess gases dissolved in steel are liberated during
solidification.

The evolution of the gas gives rise to the formation of

skin or pin holes, blow holes, pipes etc.

The unsoundness caused by these cavities affect the

mechanical properties of steel

Nitrogen pick up during steel making:

open atmosphere
raw material charged
during melting and/or refining

Effect of nitrogen in steel:

yield-point phenomena
AlN causes intergranular fracture
nitrogen stabilizes the austenitic structure

Factors affecting the nitrogen solubility in steel.

partial pressure of nitrogen in the blast

time of contact
length of after blow and
the bath temperature

[wt.%H] =

Since nitrogen dissolves atomically in liquid iron and steel

in very small proportion its solubility can be discussed in
terms of Sieverts and Henrys laws

There is slow rise in solubility in solid state with increasing

temperature but at the melting point it increases very
rapidly. It also rises in liquid steel but at a slow rate.

Presence of vanadium, niobium, tantalum, chromium,

manganese, molybdenum, and tungsten increases
nitrogen solubility in iron whereas it decreases in
presence of nickel, cobalt, silicon and carbon

Hydrogen pick up steel making:

wet solid and rusty charge materials
atmospheric humidity
wet refractory channels, runners and containers

Effect of hydrogen in steel

Decreases ductility
Appearance of hairline cracks seriously affect the
mechanical properties
Formation of blow holes and pin holes.

Water vapour coming in contact

with steel or slag leads to the
formation of hydrogen which gets
dissolved in steel melt as per
reaction:
H2O (g) = 2[H]+ [0]
At the melting point of iron
solubility in delta iron is
approximately 10 mL/ 100g.
Beyond this hydrogen will be
rejected during solidification to
produce unsound porous ingots
due to gas evolution.

Thus partial pressure of hydrogen, and composition of

steel and its temperature control the hydrogen content of
steel. According to Sieverts law solubility of hydrogen
in pure iron is expressed as:

Presence of niobium, tantalum, titanium and nickel

increases the solubility of hydrogen in iron whereas it
decreases in pressure of carbon, silicon, chromium and
cobalt.

The objectives of vacuum degassing include removal

of hydrogen from steel to avoid long annealing
treatment, removal of oxygen as carbon monoxide
and production of steels with very low carbon content
(< 0.03%).

The principle is based on the usefulness of the

Sieverts law relationship.

The equation demonstrates that subjecting the

molten steel to vacuum will decrease the hydrogen,
nitrogen as well as the oxygen content of the steel
according to the following reasons:

2[H] = H2 (g)
2[N] = N2 (g)
[C] + [O] = CO (g)

The effectiveness of vacuum treatment increases with increase in

the surface area of liquid steel exposed to vacuum.
For this purpose metal is allowed to flow in the form of thin stream
or even fall as droplets to accelerate the degassing process.

A number of methods available on commercial scale for

vacuum treatment of steel may categorized into three
groups :
1. Ladle Degassing
The teeming ladle filled with steel to one fourth of its
height is placed inside a vacuum chamber.
the melt is stirred either by bubbling argon or by
electromagnetic induction
Introduction of gas for stirring provides interface
which facilitates degassing.
In general pumping is carried out to attain the
ultimate vacuum of 1-10 mm Hg. which is supposed
to be adequate for degassing.

2.

Stream Degassing
In this case molten steel is allowed to flow
down under vacuum as a stream from the
furnace to ladle to another ladle or a mould.
A very high rate of degassing is achieved
due to large increase in surface area of
molten steel in the form of falling droplets.
Thus choice of proper vacuum pump and
vacuum chamber is important to achieve
the adequate level of degassing.

3.

Circuilation Degassing

R-H degassing process

The average rate of circulation
is
12 tons/min.
Twenty minutes are required
to
treat 100 tons of steel to bring
down 90% reduction of
hydrogen content.

D-H Vessel.

The
chamber
through 50-60
cycle time of 20
steel is exposed

is
moved
cm with a
sec. 10-15%
at a time.

7-10 cycles are required to

expose the entire steel
once.
Adequate
obtained
in 20-30
minutes.

degassing
cycles

in

is

15-20

High carbon steels like rail steels (0.65%-0.74% C, 0.6%-1.0%

Mn, 0.27-0.30% Si), ball-bearing steel (1.0% C, 1.2% Cr), etc. are
also manufactured in the LD converter by the catch carbon
technique. In this technique, dephosphorization is accelerated
and completed before decarburization. Extra lime and fluorspar
are charged and the lance is raised to a higher position for
maintaining a soft blow condition till phosphorus removal is
completed. Thereafter, decarburization is continued by a harder
blow till the bath carbon content drops to the desired level.

Alternatively, blowing may be continued to complete both

dephosphorization and decarburization. Required amount of
carburizer is then added to the low carbon steel bath to raise
the carbon content to the desired level. However, this method
involves a risk of increasing the inclusion and nitrogen
contents in the steel. These are picked up from the carburizer
(e.g., petroleum coke or graphite). For production of low alloy
steel, the alloying elements are usually added in the ladle
during tapping the steel.

As will be evident from the discussion [Mn] from the bath is

lost in the slag. (MnO) thus formed quickly combines with (SiO 2
to form (2MnO Si02). Thus, there is a reduction in the Mn
content in the bath in the initial period of the blow. As the slag
basicity increases due to lime dissolution, (MnO) is gradually
released and is reduced by carbon during intensive carbon
oxidation according to the following reactions:
(MnO) +[C] [Mn]+{CO}
[Mn] content in the bath increases again. As the intensity of the
carbon-oxygen reaction decreases towards the end of the
blow,. manganese is reoxidized from the bath. As a result, the
bath manganese content drops again. This accounts for the
characteristic 'manganese hump' in the LD converter reaction
diagram.

A basic and highly reactive slag is necessary to attain

desulphurization and dephosphorization in LD steel making at
the turndown stage. Hence the physical and chemical
characteristics of the lime used are of utmost importance.
Some common quality criteria for steel making lime are listed
below:
Chemical composition
Size distribution
Reactivity
Loss on ignition
Moisture content
Si02 in the lime reduces the CaO activity due to the formation of
larger amount of slag by fixing up about two times its mass of
CaO. This is detrimental both from "yield" and "cost" points of
view.

The sulphur content in lime should be as low as possible. An

MgO content of approximately 3.5% in lime is thought to be
beneficial because an MgO content of around 5% in the slag
has been found to hinder the formation of dicalcium silicate,
thereby ensuring a faster lime dissolution in the slag. However,
lowering of melting point and the viscosity of slag due to
increased proportion of MgO can result in early slopping. An
adequate level of MgO in slag also ensures less corrosion of
the vessel refractories because of its known properties of
neutralizing the FeO level of the bath.

Formation of slag as early as possible during the blow requires a

uniform and rapid dissolution of lime. A size range of +8 to -40 mm,
minimum proportion of fines in the lime charge and soft burnt lime
promote early slag formation. A soft burnt lime is highly porous,
having a large specific area. This results in its favorable reactivity.

Thermal dissociation reaction of unreacted CaC0 3 is endothermic. It

adversely affects the heat balance of the converter and leads to
operating problems. Similarly, a moisture content in lime directly
affects the heat balance of the vessel because of temperature losses
during its disintegration. It also acts as a potent source of hydrogen
in steel. Hence both loss on ignition (LOI) and moisture content of
lime should be low.

The lining of oxygen converters is usually made up of three

layers of bricks. First an inner layer of magnesite or burnt
dolomite brick is made. Gaps between the brick and the shell
are filled with tardolomite ramming mass. The same ramming
composition is used for making up the second intermediate
layer. The upper working layer is made of magnesia carbon
brick.
The performance of refractories is generally evaluated by the
life of the lining or by the consumption of refractories per ton of
steel produced. However, this is greatly influenced by the
severity of service conditions that prevail during operation.
In brief, these are:
Furnace atmosphere, Composition of slag, Mechanical stresses
,Thermal shock, Effect of high temperature, Geometry of the
vessels, Operational procedure or the blowing technique
Quality of hot metal, Quality of refractories.

A rapid sequence of blows, without pause, increases the lining life. A

high silicon hot metal produces a silica rich slag which increases the
wear of basic lining. At high temperature, the corrosive attack of the
slag is enhanced. Combustion of the CO generated inside the vessel
also raises the temperature in the upper zone of the furnace. This
enhances lining wear in the region. The distance of the oxygen lance
from the bath has a considerable effect on the refractory wear. Usually,
a high position of the lance leads to a reduced wear of the furnace
bottom, but it increases wear at the top and upper part of converter.
However, with the introduction of the multi-hole lance nozzles, the
oxygen is evenly distributed on the bath surface. This has solved the
problem of preferential bottom or top lining wear.

The early refractory lining for LD vessel was based generally

on doloma, magnesia or magnesia-chrome of the same quality
as used in the earlier steel making processes, e.g., Bessermer,
open hearth, etc. However, the high basicity of the LD
converter slag and the high temperature of the bath promoted
rapid wear of the refractories. Modern LD converters are,
therefore, lined with magnesia-carbon refractories. The total
Fe20s, Si02 and Al20s content in the magnesia refractory should
be low-definitely less than 4.0%-to improve its resistance to
slag attack. Sea water magnesia is usually added along with
natural magnesia to enrich the MgO content in the brick

Care would be taken to lower the B20s content in sea

water magnesia to a level at which it does not affect
the high temperature properties. The presence of
submicroscopic carbon particles in magnesia
carbon refractories inhibits penetration of slag into
the refractory.

The capacity of graphite to reduce wear is based upon its

large wetting angle for oxide melts. The melt can
penetrate the bricks only when the graphite is burnt
away. near the hot face owing to diffusion of oxygen in
between blows during a campaign. Thus, the infiltration
zone progressively advances, resulting in a continuous
wear of the lining. The slag resistance of magnesia
particles is improved by its high bulk density, low
impurity content and large crystal size of MgO particles.

LD refractory lining life has been greatly enhanced in recent years by adopting the slag splashing
technology. In this technology, a portion of the slag is retained in the vessel after tapping. A low FeO and a
high MgO slag is desirable for slag splashing. Such improvement in slag condition is achieved through
addition of dolomite lime after tapping. Slag splashing is accomplished by injecting nitrogen into a
conditioned slag at a given flow-rate and lance height. The existing oxygen-lancing equipment is used.

By varying lance height and nitrogen flow-rates, slag can be

selectively targeted and blown into particular areas of the
furnace. This is schematically illustrated in Figure given below.
The process time for slag splashing is between 1 and 4
minutes. A well-designed nitrogen slag splashing programme
can extend furnace lining life to 8,000 heats. Once slag
splashing is started, it would be done on a regular basis. Slag
splashing presents some operating challenges like lance shell

DEOXIDATION METHODS AND

PRACTICES

By
Dr. S.Sarkar
Associate Professor
Dept. of Metallurgical and
Materials Engg.
National institute of Technology,
Rourkela

PLAN OF PRESENTATION

Introduction

Deoxidation methods

Choice of deoxidisers

Removal of deoxidation product

Deoxidation equilibria

Silicon manganese deoxidation

Complex deoxidisers

Deoxidation practices

INTRODUCTION
Contrary to iron making steelmaking is practiced in
oxidizing conditions.
In all the steelmaking processes either air or oxygen is
blown or surplus air/oxygen is provided to facilitate
quick oxidation of impurities.
Under these conditions oxygen easily gets dissolved in
the steel melt.
During solidification of steel castings excess oxygen is
evolved because of very low solid solubility and is one
of causes of defective casting.
This excess oxygen has to be eliminated for production
of sound casting. The process of removal of residual
oxygen of the refined steel called deoxidation

CONT

DEOXIDATION METHODS
1.

Diffusion deoxidation
When dissolved oxygen is lowered down by
diffusion of oxygen from the steel melt to the
slag in the steelmaking furnace, the method is
called Diffusion deoxidation.
This can also be done outside the furnace under
vacuum according to the reaction:
2[O] O2 (g)
But the method can be used effectively to a
limited extent.

CONT

DEOXIDATION METHODS
2.

Precipitation deoxidation
The residual oxygen is allowed to react with
elements having higher affinity for oxygen
(compared to what iron has for oxygen) to form
oxide products.
The product being lighter than steel rises to the
top surface and can be easily removed.
Precipitation deoxidation is practiced
extensively because it is very effective in
decreasing oxygen content of steel.

PRECIPITAION DEOXIDATION CHOICES OF DEOXIDISER

Thermodynamically best
deoxidinsing element
(deoxidiser) should have the
least amount of dissolved
oxygen [O] left in equilibrium
with its own lowest
concentration in the steel
melt.
Al and Si are very effective in
deoxidation of steel and
hence they are used
extensively.
Al, Si and Mn are reasonably
cheap and hence used as
common deoxidizers.

CHOICE OF DEOXIDISER
Some times Zr, Ti, V, Nb etc. are used in
deoxidation of steel but they are costlier than
common deoxidisers.
The residual content of the deoxidiser in steel
after deoxodation should not adversely affect the
mechanical properties of steel.
The rate of deoxidation i.e. formation of oxide
products must be fast.
Since kinetic data on deoxidation are very limited
thermodynamic consideration play major role in
selection of deoxidisers and estimation of residual
content of the deoxidisers in steel at the end of
deoxidation.

REMOVAL OF DEOXIDATION
PRODUCTS

The mechanically entrapped oxide products in steel are

called nonmetallic inclusions which deteriorate the
mechanical properties.
Size, shape, distribution and chemical composition of
inclusions make effective contribution in controlling
the properties of steel.
This makes it essential to remove the deoxidation
products from the steel melt to get clean steel.
Thus from cleanliness point of view a gaseous product
of deoxidation would be most appropriate.

REMOVAL OF DEOXIDATION
PRODUCTS
Only carbon produces gaseous deoxidation
product under reduced pressure according to the
reaction:
[ C ] + [ O ] = CO ( g )
Though the reaction is favoured under reduced
pressure but economics do not permit for vacuum
treatment.
Hence carbon cannot be used as a deoxidiser for
production of clean steel.
Deoxidisers other than carbon form liquid or solid
products.

REMOVAL OF DEOXIDATION
PRODUCTS

Formation of a solid deoxidation product will give rise to a

new phase which will grow during the course of deoxidation
and has to rise to surface of the melt for elimination.
Otherwise it will disperse in the melt and on solification
may be entrapped in steel as nonmetallic inclusions.
For nucleation and growth of deoxidation products required
interface may be provided by inhomogenities, for example
formation of Al2O3/steel interface while deoxidising steel
with aluminium at the beginning.

REMOVAL OF DEOXIDATION
PRODUCTS
The rate of rise of the decoxidation product (v) in a quiet
bath may be estimated from Stokes law:

Where g, r, liq, dp and stand respectively for acceleration

due to gravity, radius of the deoxidation product, densities
of the liquid metal and the deoxidation product and the
viscosity of the liquid metal.
that r2 factor plays an important role in controlling the time
required for the particles to rise to the surface of the
metallic bath.

REMOVAL OF DEOXIDATION
PRODUCTS

On the basis of Stokes law it can be

demonstrated that particles of deoxidation
product less than 0.001cm radius will not move to
the surface of the metallic bath in a usual ladle
within the normal holding time of 20 minutes,
whereas larger particles ( radius greater than
0.01cm) should be completely eliminated.
These figures emphasise the significance of
coalescence of deoxidation products in formation
of particles of larger radius to facilitate rapid rise
to the surface of the steel melt

REMOVAL OF DEOXIDATION
PRODUCTS

Since coalescence of the deoxidation product is

more likely in liquid state, deoxidation is often
carried out to obtain liquid products.
The rate of removal is also affected by the
interfacial energy between the liquid metal and
the deoxidation product.
High interfacial energy will enhance the rate of
removal of the product by lowering the dragging
affect.

REMOVAL OF DEOXIDATION
PRODUCTS

The rate of rise of the decoxidation product (v) in a

quiet bath may be estimated from Stokes law:
Where g, r, liq, dp and stand respectively for
acceleration due to gravity, radius of the deoxidation
product, densities of the liquid metal and the
deoxidation product and the viscosity of the liquid
metal.
that r2 factor plays an important role in controlling the
time required for the particles to rise to the surface of
the metallic bath.

for which the equilibrium constant is given as :

DEOXIDATION EQUILIBRIA

A generalised form of chemical equilibrium dealing

with the deoxidation product in contact with steel melt
may be represented as:
x [M] + y [O] = MxOy (s, l )

By and large all the solid deoxidation products except

Fe(Mn)O have stoichiometric compositions.
Since we are dealing with infinitely dilute solutions of
deoxidisers in the melt according to Henrys law we
can write

DEOXIDATION EQUILIBRIA

The activity coefficient of oxygen decreases and

that of alloying element increase, with increases
in concentration of the alloying element.
However the minimum oxygen content decreases
with the increasing stability of the deoxidation
product.

SILICON MANGANESE
DEOXIDATION

Deoxidation is most widely carried out by common

deoxidisers like silicon and manganese.
The deoxidation with manganese giving rise to the
formation of liquid or solid solution of FeO and MnO
may be represented as:
[Mn] + (FeO) ( s, l ) = [Fe] ( l ) + (MnO) ( s, l )
Deoxidation by silica is given by
[Si] + 2 [O] = (SiO2)
Deoxidation with silicon is much more effective as
compared to manganese but simultaneous deoxidation
by both the elements leaves much lower residual oxygen
in the melt due to reduced activity of SiO 2 in FeO MnO
SiO2 slag.

SILICON MANGANESE
DEOXIDATION

Assuming that the deoxidation product is pure

manganese silicate and the sum of the deoxidation
reactions by silicon and manganese are represented as:
[Si] + 2 (MnO) = 2 [Mn] + ( SiO2 )

The figure highlights the role of manganese in

boosting5 the deoxidising power of silicon with
increasing silicon content.
For example at 0.05% Si in solution, the residual
oxygen is lowered from 0.023% to 0.016% when the
manganese content is increased from zero to 0.8% ;
while at 0.2% Si, a similar increase in manganese
lowers the residual oxygen from 0.0104% to 0.0094%6.

SILICON MANGANESE
DEOXIDATION

Simultanious deoxidation by silicon and

manganese at 1600oC.

SILICON MANGANESE
DEOXIDATION
Residual oxygen and
silicon contents of iron
after deoxidation of 0.10
% oxygen steel at 1650oC
at various residual
manganese contents
from 0.2 to 0.6 % Mn.

SILICON MANGANESE
DEOXIDATION

From the figure it is evident that at all temperatures

for the metal compositions lying above the curve,
manganese does not take part in deoxidation reaction
and solid silica is formed.
On the other hand metal composition lying below the
curve the deoxidation product is liquid manganese
silicate whose composition is controlled by the ratio [%
Si]/[% Mn]2 in the metal.
From the above discussion it is clear that silicon alone
is a very effective deoxidiser but it produces solid
product which poses problems in separation from the
steel melt.

SILICON MANGANESE
DEOXIDATION

Though manganese is not effective it produces

liquid deoxidation product. Both silicon and
manganese used together give better result.

SILICON MANGANESE
DEOXIDATION

Deoxidation first carried out by addition of

ferromanganese in steel melt produces FeO MnO
liquid slag which dissolves SiO2 when ferrosilicon
deoxidises the melt in second step.

In the resulting slag FeO MnO SiO2 the activities of

SiO2 and MnO are much lower than when FeMn and
FeSi are used separately for deoxidation.
Lowering of activity improves their effectiveness in
reducing the residual oxygen in steel when Mn and Si
are added in correct proportion.

SILICON MANGANESE
DEOXIDATION
In practice the ratio (Mn/Si) is normally maintained
between 7 and 4 to obtain a thin liquid slag as the
deoxidation product.

At 16000C the equilibrium oxygen level is

approximately 0.1% with 0.5% Mn but addition of 0.1%
Si reduces residual oxygen to 0.015%.

OTHER
DEOXIDISERS
Aluminum is even more effective deoxidiser as it has more

affinity for oxygen compared to silicon and manganese. But

it cannot be used alone to deoxidise steel completely because
the deoxidation product, Al2O3 is solid at the steelmaking
temperature.

While using along with manganese and silicon alumina will

dissolve in the liquid slag product of deoxidation. Boron,
titanium and zirconium are also very effective deoxidisers.
The extent of deoxidation achieved by 8% Si can be easily
obtained by 0.7% B, or 0.1% Ti or 0.002% Al or 0.00003% Zr.

COMPLEX
DEOXIDISERS
The rare earth elements or alloys based on them are

employed in conjunction with common deoxidisers for

bringing down sulphur and oxygen to a low desired level.

A commercial rare earth mixture, known as REM

containing 48-50% Ce, 32-34% La, 13-14% Nd, 4-5% Ps,
and 0.6-1.6% higher lanthanides has been reported.
For achieving low residual oxygen in steel the complex
deoxidisers must exhibit

low vapour pressure

Liquid deoxidation products

COMPLEX
DEOXIDISERS

Dissolution in steel calcium silicide reacts with oxygen

to form molten calcium silicate slag which can flux
alumina inclusion.

Possessing similar characteristics an alloy of Ca, Si, Al

and Ba is a good deoxidiser to produce clean steel.
Occasionally the deoxidation products are beneficial if
they remain entrapped in a very finely dispersed form.
For example, very fine dispersion of Al2O3 particles
without coagulation provides the possible nucleation
sites during solidification of steel resulting in a very
fine grain structure of steel.

DEOXIDATION PRACTICE

On industrial scale there are three methods of

deoxidation.
After refining, molten steel can be deoxidized either
inside the furnace, called furnace deoxidation or
during tapping in a ladle, called ladle deoxidation.
For production of fine grained steel or in case of
inadequate deoxidation a small portron of total
deoxidation may be done in the ingot moulds.

DEOXIDATION PRACTICE
As deoxidation lowers the oxidizing potential of
the bath there is a fair chance of reversion of the
refining reactions if oxidised refining slag is
present in contact with the metal.
Stable oxides like SiO2 and MnO are not prone to
reversion in acid steelmaking processes.
However P2O5 in basic steelmaking is very easily
reduced from the slag to the metal phase on drop
of oxygen potential.

DEOXIDATION PRACTICE

In general the refining slag is flushed off in basic

process and deoxidation may be carried out
partly in the furnace and major part in the ladle.

As products of deoxidation in a furnace get more

time to reach the surface of the bath furnace
deoxidation is useful in production of clean steel.

CONTROL OF INGOT STRUCTURE

The final structure of an ingot is entirely determined

by the degree of deoxidation carried out prior to
solidification of steel in a mould.
The residual oxygen in the steel at the end of refining
is determined by the steel making practice and the
type of steel produced.
For a given type of steel the steel making and
deoxidation practices have to properly adjusted to
finally obtain the desired ingot structure.

RIMMING
STEEL

Rimming steel require a lot of gas evolution during

solidification. The steel, therefore, must contain
enough dissolved oxygen and which is possible only in
low carbon steel (<0.15%).

The heat must be finished in the furnace in such a way

that the bath contains desired level of oxygen having
carbon level < 0.15%.
In general, no deoxidation is carried out inside the
furnace. Only a small amount of deoxidation is carried
out in the ladle using Fe-Mn and Al.

RIMMING STEEL

The zone between the

primary and secondary
blow holes is called rim
which is characteristics of
rimming ingots.
Rimming ingot is
relatively cleaned due to
less inclusions and brisk
evolution of gas in the
beginning of
solidification.

SEMI-KILLED STEEL
These are partially deoxidised steel such that
only small amount of gas is evolved during
solidification.
The carbon content has been in the range of 0.150.30%.
Partial deoxidation is carried out in the furnace
itself using Fe-Mn and Al.
The gas is evolved towards the end of the
solidification. The blow holes are therefore,
present in the middle and top of the ingot.

SEMI-KILLED STEEL

Aluminium is put into

the ladle toward the
end of pouring to
completely deoxidises
the top of the ingot to
compensate the pipe
formation.

KILLED STEEL
No gas evolution take place in killed steel during
solidification.
All steels containing 0.3% C are killed.
The heat is worked in such a way that by the
time carbon level drops close to specification level
the refining should be over.
In general the heat is then blocked by adding FeSi, Fe-Mn and high silicon pig iron.
Blocking stops the carbon oxygen reaction by
lowering oxygen content of the bath

KILLED STEEL

Deoxidation product should

be given sufficient time to
rise to the surface
otherwise it will form
nonmetallic inclusions in
steel.
Solidification of Killed steel
is accompanied by V or A
type seggregation

ADVANCES IN STEELMAKING
AND SECONDARY
STEELMAKING
Smarajit Sarkar
Department of Metallurgical and Materials
Engineering
NIT Rourkela

As a standard guide the temperature rise attainable by

oxidation of 001 % of each of the element dissolved in
liquid iron at 1400C by oxygen at 25C is calculated
assuming that no heat is lost to the surroundings and
such data are shown below
.

OXYGEN BOTTOM MAXHUTTE PROCESS(OBM)

BOTTOM BLOWING VS TOP BLOWING

Oxidation of carbon : Bottom blowing increases sharply the
intensity of bath stirring and increases the area of gas-metal
boundaries (10-20 times the values typical of top blowing) .

Since the hydrocarbons supplied into the bath together with

oxygen dissociate into H2, H2O and CO2 gas bubbles in the
bath have a lower partial pressure of carbon monoxide (Pco )

All these factors facilitate substantially the formation and

evolution of carbon monoxide, which leads to a higher rate of
decarburization in bottom blowing

CONT..

The degree of oxidation of metal and slag

Removal of phosphorous: Since the slag of the bottomblown converter process have a low degree of oxidation
almost during the whole operation, the conditions
existing during these periods are unfavorable for
phosphorus removal

SEQUENCE OF ELIMINATION OF
IMPURITIES IN OBM PROCESS

SLOPPING

Problems arise when the layer of foaming slag created on the

surface of the molten metal exceeds the height of the vessel and
overflows, causing metal loss, process disruption and environmental
pollution. This phenomenon is commonly referred to as slopping.

METALLURGICAL FEATURES OF BATH

AGITATED PROCESS:

Better mixing and homogeneity in the bath offer the following

advantages:

Less slopping, since non-homogeneity causes formation of regions with

high supersaturation and consequent violent reactions and ejections.

Better mixing and mass transfer in the metal bath with closer approach
to equilibrium for [C]-[O]-CO reaction, and consequently, lower bath
oxygen content at the same carbon content

Better slag-metal mixing and mass transfer and consequently,

closer approach to slag- metal equilibrium, leading to:
o lower FeO in slag and hence higher Fe yield
o transfer of more phosphorus from the metal to the slag (i.e.
better bath dephosphorisation)
o transfer of more Mn from the slag to the metal, and thus
better Mn recovery
o lower nitrogen and hydrogen contents of the bath.
More reliable temperature measurement and sampling of
metal and slag, and thus better process control
Faster dissolution of the scrap added into the metal bath

HYBRID BLOWING
A

small amount of inert gas, about 3% of the volume of oxygen

blown from top, introduced from bottom, agitates the bath so

effectively that slopping is almost eliminated.
However

for obtaining near equilibrium state of the system

inside the vessel a substantial amount of gas has to be

introduced from the bottom.
If

20-30% of the total oxygen, if blown from bottom, can cause

adequate stirring for the system to achieve near equilibrium

conditions. The increase beyond 30% therefore contributes
negligible addition of benefits.

CONT..

The more the oxygen fraction blown from bottom the

less is the post combustion of CO gas and consequently
less is the scrap consumption in the charge under
identical conditions of processing.

Blowing of inert gas from bottom has a chilling effect on

bath and hence should be minimum. On the contrary the
more is the gas blown the more is the stirring effect and
resultant better metallurgical results. A optimum choice
therefore has to be made judiciously.

CONT..
As compared to top blowing, the hybrid blowing
eliminates the temperature and concentration
gradients and effects improved blowing control,
less slopping and higher blowing rates. It also
reduces over oxidation and improves the yield. It
leads the process to near equilibrium with resultant
effective dephosphorisation and desulphurisation
and ability to make very low carbon steels.

 What

is blown from the bottom, inert gas or oxygen?

How much inert gas is blown from the bottom?
At what stage of the blow the inert gas is blown,
although the blow, at the end of the blow, after the blow
ends and so on?
What inert gas is blown, argon, nitrogen or their
combination?
How the inert gas is blown, permeable plug, tuyere, etc.?
What oxidising media is blown from bottom, oxygen or
air?
If oxygen is blown from bottom as well then how much of
the total oxygen is blown from bottom ?

THE VARIETY OF HYBRID PROCESSES ALONG

WITH AMOUNT OF BASAL GAS INJECTED

METALLURGICAL
SUPERIORITY OF
The processes have been developed to obtain the combined advantages of
HYBRID BLOWING
both LD and OBM to the extent possible. Therefore the metallurgical

performance of a hybrid process has to be evaluated in relation to these two

extremes, namely the LD and the OBM. The parameters on which this can
be done are :

Iron content of the slag as a function of carbon content of bath

Oxidation levels in slag and metal

Manganese content of the bath at the turndown

Desulphurisation efficiency in terms of partition coefficient

Dephosphorisation efficiency in terms of partition coefficient

Hydrogen and nitrogen contents of the bath at turndown

Yield of liquid steel

DEOXIDATION OF STEEL
The oxidizing conditions of a heat in a steelmaking plant, the
presence of oxidizing slag, and the interaction of the metal with the
surrounding atmosphere at tapping and teeming - all these factors
are responsible for the fact that the dissolved oxygen in steel has a
definite, often elevated, activity at the moment of steel tapping. The
procedure by which the activity of oxygen can be lowered to the
required limit is called deoxidation. Steel subjected to deoxidation is
termed 'deoxidized'. If deoxidized steel is 'quiet during solidification
in moulds, with almost no gases evolving from it, it is called 'killed
steel'.

If the metal is tapped and teemed without being deoxidized, the reaction
[O] + [C] = COg will take place between the dissolved oxygen and
carbon as the metal is cooled slowly in the mould. Bubbles of carbon
monoxide evolve from the solidifying metal, agitate the metal in the
mould vigorously, and the metal surface is seen to 'boil'. Such steel is
called 'wild'; when solidified, it will be termed 'rimming steel' .

In some cases, only partial deoxidation is carried out, i.e. oxygen is only
partially removed from the metal. The remaining dissolved oxygen
causes the metal to boil for a short time. This type of steel is termed
'semi-killed'.

Thus, practically all steels are deoxidized to some or other extent so as

to lower the activity of dissolved oxygen to the specified limit.

The activity of oxygen in the metal can be lowered by two methods: (I)
by lowering the oxygen concentration, or
(2) by combining oxygen into stable compounds.

There are the following main practical methods for deoxidation of steel:
(a) precipitation deoxidation, or deoxidation in the bulk;
(b) diffusion deoxidation;
(c) treatment with synthetic slags; and
(d) vacuum treatment.

The upper part containing the exposed pipe in killed

steels has to be rejected and this decreases the yield
to about 80 %. The yield from a rimmed ingot is
higher.
Only a killed steel can be continuously cast. In
contrast to ingot steel, the yield in continuous casting
is more than 90 %. A rimmed steel cannot be
continuously cast, as the rimming action can puncture
holes through the thin solidified layer of the cast slab
and the liquid steel may pour out uncontrollably.
The turbulence during gas evolution in a rimmed
ingot physically transports the metal to different
parts, causing macrosegregation to a greater extent.

CONTINUOUS CASTING
The advantages of continuous casting (over ingot
casting) are:
It is directly possible to cast blooms, slabs and
billets, thus eliminating blooming, slabbing mills
completely, and billet mills to a large extent.
Better quality of the cast product.
Higher crude-to-finished steel yield (about 10 to
20% more than ingot casting).
Higher extent of automation and process control.

SIMPLIFIED SKETCH OF
CONTINUOUS CASTING

THE MAJOR REQUIREMENTS OF CONTINUOUS

CASTING

Solidification must be completed before the withdrawal

rolls.

The liquid core should be bowl-shaped as shown in the

Figure and not pointed at the bottom (as indicated by the
dotted lines), since the latter increases the tendency for
undesirable centerline (i.e. axial) macro-segregation and
porosity

The solidified shell of metal should be strong enough at

the exit region of the mould so that it does not crack or
breakout under pressure of the liquid.

METALLURGICAL COMPARISON OF
CONTINUOUS CASTING WITH INGOT
CASTING

The surface area-to-volume ratio per unit length of

continuously cast ingot is larger than that for ingot
casting. As a consequence, the linear rate of
solidification (dx/dt) is an order of magnitude higher
than that in ingot casting.

The dendrite arm spacing in continuously cast

products is smaller compared with that in ingot
casting.

CONT

Macro-segregation is less, and is restricted to the

centreline zone only.

Endogenous inclusions are smaller in size, since they

get less time to grow. For the same reason, the blow
holes are, on an average, smaller in size.

Inclusions get less time to float-up. Therefore, any nonmetallic particle coming into the melt at the later stages
tends to remain entrapped in the cast product.

In addition to more rapid freezing, continuous casting differs from

ingot casting in several ways. These are noted below.
Mathematically speaking, continuously cast ingot is infinitely long.
Hence, the heat flow is essentially in the transverse direction,
and there is no end-effect as is the case in ingot casting (e.g.
bottom cone of negative segregation, pipe at the top, etc.).

The depth of the liquid metal pool is several metres long. Hence,
the ferrostatic pressure of the liquid is high during the latter
stages of solidification, resulting in significant difficulties of blowhole formation.

Since the ingot is withdrawn continuously from the mould, the frozen
layer of steel is subjected to stresses. This is aggravated by the
stresses arising out of thermal expansion/ contraction and phase
transformations.

Such stresses are the highest at the surface. Moreover, when the ingot
comes out of the mould, the thickness of the frozen steel shell is not
very appreciable. Furthermore, it is at around 1100-1200C, and is
therefore, weak. All these factors tend to cause cracks at the surface
of the ingot leading to rejections.

Use of a tundish between the ladle and the mould results in extra
temperature loss. Therefore, better refractory lining in the ladles,
tundish, etc. are required in order to minimise corrosion and erosion by
molten metal.

SECONDARY STEELMAKING

Smarajit Sarkar
Department of Metallurgical and Materials
Engineering
NIT Rourkela

SECONDARY STEELMAKING
Primary steelmaking is aimed at fast melting
and rapid refining. It is capable of refining at
a macro level to arrive at broad steel
specifications, but is not designed to meet
the stringent demands on steel quality, and
consistency of composition and temperature
that is required for very sophisticated grades
of steel. In order to achieve such
requirements, liquid steel from primary
steelmaking units has to be further refined in
the ladle after tapping. This is known as
Secondary Steelmaking.

SECONDARY STEELMAKING IS
RESORTED TO ACHIEVE ONE OR MORE
OF THE FOLLOWING REQUIREMENTS :
improvement

in quality
improvement in production rate
decrease in energy consumption
use of relatively cheaper grade or
alternative raw materials
use of alternate sources of energy
higher recovery of alloying elements.

QUALITY OF STEEL
Lower

impurity contents .
Better cleanliness. (i.e. lower inclusion
contents)
Stringent quality control. (i.e. less
variation from heat-to-heat)
Microalloying to impart superior
properties.
Better surface quality and
homogeneity in the cast product.

CLEAN STEEL
The

term clean steel should mean a

steel free of inclusions. However, no
steel can be free from all inclusions.
Macro-inclusions are the primary
harmful ones. Hence, a clean steel
means a cleaner steel, i.e., one
containing a much lower level of
harmful macro-inclusions.)

INCLUSIONS

In practice, it is customary to divide

inclusions by size into macro inclusions and
micro inclusions. Macro inclusions ought to
be eliminated because of their harmful
effects. However, the presence of micro
inclusions can be tolerated, since they do
not necessarily have a harmful effect on the
properties of steel and can even be
beneficial. They can, for example, restrict
grain growth, increase yield strength and
hardness, and act as nuclei for the
precipitation of carbides, nitrides, etc.

MACRO AND MICRO

INCLUSIONS
The critical inclusion size is not fixed but
depends on many factors, including service
requirements.
Broadly speaking, it is in the range of 5 to
500 m (5 X 10-3 to 0.5 mm). It decreases
with an increase in yield stress. In highstrength steels, its size will be very small.
Scientists advocated the use of fracture
mechanics concepts for theoretical
estimation of the critical size for a specific
situation.

SOURCES OF INCLUSIONS

Precipitation due to reaction from molten steel or during

freezing because of reaction between dissolved oxygen
and the deoxidisers, with consequent formation of oxides
(also reaction with dissolved sulphur as well). These are
known as endogenous inclusions.
Mechanical and chemical erosion of the refractory lining
Entrapment of slag particles in steel
Oxygen pick up from the atmosphere, especially during
teeming, and consequent oxide formation.
Inclusions originating from contact with external sources
as listed in items 2 to 4 above, are called exogenous
inclusions.

REMOVAL OF
INCLUSIONS
With a lower wettability (higher value of Me
inc

), an inclusion can be retained in contact

with the metal by lower forces, and therefore,

can break off more easily and float up in the
metal. On the contrary, inclusion which are
wetted readily by the metal, cannot break off
from it as easily.

CLEANLINESS CONTROL DURING

DEOXIDATION
Carryover slag from the furnace into the ladle
should be minimised, since it contains high
percentage of FeO + MnO and makes efficient
deoxidation fairly difficult.

Deoxidation products should be chemically

stable. Otherwise, they would tend to
decompose and transfer oxygen back into liquid
steel. Si02 and Al203 are preferred to MnO.
Moreover the products should preferably be
liquid for faster growth by agglomeration and
hence faster removal by floatation. Complex
deoxidation gives this advantage.

CONT
Stirring

of the melt in the ladle by argon flowing through

bottom tuyeres is a must for mixing and homogenisation,
faster growth, and floatation of the deoxidation products.
However, very high gas flow rates are not desirable from the
cleanliness point of view, since it has the following adverse
effects:

Too vigorous stirring of the metal can cause disintegration of

earlier formed inclusion conglomerates.

Re-entrainment of slag particles into molten steel.

Increased erosion of refractories and consequent generation

of exogenous inclusions.

More ejection of metal droplets into the atmosphere with

consequent oxide formation.

THE SPEED OF FLOATING OF LARGE

INCLUSION CAN BE FOUND BY STOKES
FORMULA

PROCESS VARIETIES
The varieties of secondary steelmaking processes
that have proved to be of commercial value can
broadly be categorised as under:
Stirring treatments
Synthetic slag refining with stirring
Vacuum treatments
Decarburisation techniques
Injection metallurgy
Plunging techniques
Post-solidification treatments.

VARIOUS SECONDARY PROCESS

AND THEIR CAPABILITIES

VACUUM DEGASSING PROCESSES

Ladle degassing processes (VD, VOD,

VAD)

Stream degassing processes

Circulation degassing processes (DH and

RH).

SKETCH OF A RH
DEGASSER

RH DEGASSER

Molten steel is contained in the ladle. The two legs of the vacuum
chamber (known as Snorkels) are immersed into the melt. Argon is
injected into the up leg.

Rising and expanding argon bubbles provide pumping action and lift the
liquid into the vacuum chamber, where it disintegrates into fine droplets,
gets degassed and comes down through the down leg snorkel, causing
melt circulation.

The entire vacuum chamber is refractory lined. There is provision for

argon injection from the bottom, heating, alloy additions, sampling and
sighting as well as video display of the interior of the vacuum chamber.

RH-OB PROCESS

Why RH-OB Process?

To meet increasing demand for cold-rolled steel sheets with improved
mechanical properties, and to cope with the change from batch-type to
continuous annealing, the production of ULC steel (C < 20 ppm) is
increasing.
A major problem in the conventional RH process is that the time
required to achieve such low carbon is so long that carbon content at
BOF tapping should be lowered. However, this is accompanied by
excessive oxidation of molten steel and loss of iron oxide in the slag.
It adversely affects surface the quality of sheet as well.

Hence, decarburization in RH degasser is to be speeded up.

This is achieved by some oxygen blowing (OB) during degassing.
The RH-OB process, which uses an oxygen blowing facility
during degassing, was originally developed for decarburization
of stainless steel by Nippon Steel Corp., Japan, in 1972.
Subsequently, it was employed for the manufacture of ULC
steels.
The present thrust is to decrease carbon content from
something like 300 ppm to 10 or 20 ppm within 10 min.
Cont

AOD PROCESS

AOD PROCESS

Conventional AOD, no top blowing is involved. Only

a mixture of argon and oxygen is blown through the
immersed side tuyeres. However, the present AOD
converters are mostly fitted with concurrent facilities
for top blowing of either only oxygen, or oxygen
plus inert gas mixtures using a supersonic lance as
in BOF steelmaking.

CONT..

Initially, when the carbon content of the melt is high, blowing

through the top lance is predominant though the gas mixture
introduced through the side tuyeres also contains a high
percentage of oxygen.

However, as decarburisation proceeds, oxygen blowing from

the top is reduced in stages and argon blowing increased. As
stated earlier, some stainless steel grades contain nitrogen as
a part of the specifications, in which case, nitrogen is
employed in place of argon in the final stages.

THERMODYNAMICS OF REACTIONS IN THE

AOD PROCESS

Simplified by Hiltey and Kaveney

INFLUENCE OF PRESSURE AND TEMPERATURE

ON THE RETENTION OF CR BY OXYGEN
SATURATED STEEL MELTS AT 0.05%C

COREX SMELTING REDUCTION

PROCESS

This process produces molten iron in a two-step reduction melting

operation. One reactor is melter-gasifier and the other is prereducer. In the pre-reducer, iron oxide is reduced in counter-flow
principle. The hot sponge is discharged by screw conveyors into the
melting reactor.

Coal is introduced in the melting-gassifying zone along with

oxygen gas at the rate of 500-600 Nm3/thm. The flow velocity is
chosen such that temperature in the range of 1500-1800C is main
tained. The reducing gas containing nearly 85% CO is hot dedusted
and cooled to 800-900C before leading it into the pre-reducer

FINEX PROCESS

FINEX PROCESS

In the FINEX Process fine ore is preheated and reduced to DRI in a

train of four or three stage fluidized bed reactors.

The fine DRI is compacted and then charged in the form of Hot
Compacted Iron (HCI) into the melter gasifier. So, before charging to
the melter- gasifier unit of the FINEX unit, this material is compacted
in a hot briquetting press to give hot compacted iron (HCI)

since the melter- gasifier can not use fine material (to ensure
permeability in the bed).

Non-coking coal is briquetted and is fed to the melter gasifier where

it is gasified with oxygen

As a standard guide the temperature rise attainable by

oxidation of 001 % of each of the element dissolved in
liquid iron at 1400C by oxygen at 25C is calculated
assuming that no heat is lost to the surroundings and
such data are shown below
.

Ahindra Ghosh and Amit Chatterjee: Ironmaking and Steelmaking Theory and Practice, PrenticeHall of India Private Limited, 2008

Anil K. Biswas: Principles of Blast Furnace Ironmaking, SBA Publication,1999

R.H.Tupkary and V.R.Tupkary: An Introduction to Modern Iron Making, Khanna Publishers.

R.H.Tupkary and V.R.Tupkary: An Introduction to Modern Steel Making, Khanna Publishers.

David H. Wakelin (ed.): The Making, Shaping and Treating of Steel (Ironmaking Volume), The AISE
Steel Foundation, 2004.

Richard J.Fruehan (ed.): The Making, Shaping and Treating of Steel (Steeelmaking Volume), The
AISE Steel Foundation, 2004.

A.Ghosh, Secondary Steel Making Principle & Applications, CRC Press 2001.

R.G.Ward: Physical Chemistry of iron & steel making, ELBS and Edward Arnold, 1962.

F.P.Edneral: Electrometallurgy of Steel and Ferro-Alloys, Vol.1 Mir Publishers,1979

B. Ozturk and R. J. Fruehan,: "Kinetics of the Reaction of SiO(g) with Carbon Saturated Iron":
Metall. Trans. B, Vol. 16B, 1985, p. 121.

B. Ozturk and R. J. Fruehan: "The Reaction of SiO(g) with Liquid Slags,

17B, 1986, p. 397.

B. Ozturk and R. J. Fruehan:.Transfer of Silicon in Blast Furnace": , Proceedings of the fifth

International Iron and Steel Congress, Washington D.C., 1986, p. 959.

P. F. Nogueira and R. J. Fruehan: Blast Furnace Softening and Melting Phenomena - Melting Onset
in Acid and Basic Pellets", , ISS-AIME lronmaking Conference, 2002, pp. 585.

Metall. Trans.B, Volume

Paulo Nogueira, Richard Fruehan: "Blast Furnace Burden Softening and Melting
Phenomena-Part I Pellet Bulk Interaction Observation", , Metallurgical and Materials
Transactions B, Volume 35B, 2004, pp. 829.

P.F. Nogueira, Richard J. Fruehan: 'Fundamental Studies on Blast Furnace Burden

Softening and Melting", Proceedings of 2nd International Meeting on lronmaking,
September 2004, Vitoria, Brazil.

Paulo F. Nogueira, Richard J. Fruehan, "Blast Furnace Softening and Melting

Phenomena - Part III: Melt Onset and Initial Microstructal Transformation in Pellets",
submitted to Materials and Metallurgical Transactions B.

Paulo F. Nogueira, Richard J. Fruehan :Blast Furnace Burden Softening and Melting
Phenomena-Part II Evolution of the Structure of the Pellets", Metallurgical and
Materials Transactions, Volume 36B, 2005, pp. 583

MA Jitang: Injecuion of flux into Blast Furnace via Tuyeres for optimizing slag
formation ISIJ International, Volume 39, No7 1999,pp697

Y.S.Lee, J.R.Kim, S.H.Yi and D.J.Min: Viscous behavior of CaO-SiO2-Al2O3-MgOFeO Slag, Proceedings of VIIInternational Conferenceon -Molten slags,fluxes and
salts, The South African Institute of Minig and Metallurgy, 2004,pp225

THANK YOU

DESIGN OF BLAST
FURNACE
Smarajit Sarkar
Department of Metallurgical and Materials
Engineering
NIT Rourkela