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Module 1: Steelmaking Fundamentals

Lecture 1: Types of steels, History of modern steelmaking and Indian scenario

The Lecture Contains:


Attributes
Types of Steels
Effect of impurity elements
Historical Perspectives
Present Status of Steel Industry
Attributes:
Steel belongs to iron carbon system. This system has a unique feature to alloy with several elements of the periodic
table to produce materials for diversified applications.
Iron-Carbon system is capable of creating any desired property by altering the microstructure through surface
hardening, heat treatment and deformation processing.
Steel is recyclable and hence is a green material.
The above attributes make steel to be the most important engineering material. Around 2500 different grades are
produced to cater the need of several industries ranging from structural to aero-space.

Types of steels: Below are given some applications. Details can be looked into references given at the end of
the lecture.
Broadly we have either plain carbon (carbon is the principle alloying element) or alloy (in addition to carbon
there are other alloying elements like Nb, V, W, Cr, Ni etc) steel. Plain carbon steels are the following types:
Properties

Low carbon

Medium carbon

High carbon

Carbon

Lower than 0.25


weight
Percent

In between 0.25 and


0.6 weight percent

In between 0.6 and 1.4


weight percent

Some
properties

Excellent ductility Low hardenabilty.


Hardest,strongest and
and
Least ductile
toughness.
These steel grades can
Weldableand
be heat treated
machinable
Not amenable to
Martensite
transformation

Some
Common products For higher strength
applications like
suchas in machinery,
Nuts, bolts, sheets
etc.
Automobiles and agriccultural parts (gears,
axels, connecting rods)
etc.

Used where
strength,hardness
and wear resistance
is required.
Cutting tools, cable,
Musical wires etc.

The alloy steels are classified as low (less than 5 weight% alloying elements), medium (in between 5 to 10
weight percent alloying elements) and high alloy steels (more than 10 weight percent alloying elements).
Note: Whether plain carbon or alloyed ones, all steels contain impurities like sulphur, phosphorus, hydrogen,
nitrogen, oxygen, silicon and manganese, tramp elements like copper, tin, antimony, and non-metallic
inclusions. These impurities are to be controlled during steelmaking
Effect of impurity elements on steel properties (some effects are given; details can be seen in the
references given at the end of this lecture)
Carbon imparts strength to iron. It reduces ductility and impact strength. But presence of carbon allows heat
treatment procedures.
Sulphur segregates during solidification (segregation coefficient is 0.02). Sulphur causes hot shortness due to
formation of FeS formed during solidification of steel. Sulphide inclusions lower weldability and corrosion
resistance. Presence of sulphur may also lead to development of tear and cracks on reheating the steel.
Phosphorus segregates during solidification (segregation coefficient is 0.02). Presence of phosphorus impairs
plastic properties.
Silicon and manganese: Silicon reduces the drawing capacity of steel. Manganese is beneficial; it increases
strength without affecting ductility and sharply reduces hot shortness.
Gases: Nitrogen impairs plastic properties and increases embrittlement at lower temperatures. Hydrogen causes
defects such as flakes, fish-scale fracture.
Inclusions: Presence of inclusions at the grain boundary weakens intra-granular bonds. Inclusions also act as
stress concentrators. Some type of inclusions is brittle.
Tramp elements: Tramp elements like copper, zinc, tin, antimony etc create problems during reheating of steels
because their melting points are much lower than steel reheat temperature.

Historical Perspectives:
Year

Developments

1856

Henry Bessemer developed a process for bulk steel production. He


blew air in an

acid lined pear shaped vessel. The process is termed Acid Bessemer
Process. No heat was supplied from outside. It did not become
possible for him to remove S and P. Moreover oxygen content of
steel was high. Hot shortness was a problem during rolling.
1878

S.G.Thomas and Gilchrist developed basic Bessemer process. They


lined the vessel with basic refractory. High nitrogen content of steel,
no usage of scrap and plugging of bottom blown tuyeres were the
problems.

1868

Siemenss and Martins developed Open Hearth Process. In this


process thermal energy was supplied through combustion of gaseous
and liquid fuels thus enabling them to use steel scrap in addition to
other charge materials. Open Hearth Process for steelmaking has
dominated the steel production for over approximately a century.

1900

Paul Heroult showed use of electricity for steel production. The


quality of steel was better than open hearth process. The process was
mainly used to produce alloy and special steels from scrap.

1950

Oxygen was used to produce steel at Linz and Donawitz and process
was termed LD Converter steelmaking. Oxygen was supplied
through a consumable single hole lance from top of a pear shaped
vessel.

1960

Continuous casting was developed. Today most of the steel plants


use continuous casting to produce billet/bloom/slab

1970
and
till
date

Major developments took place in the following areas

Multi-hole lances for blowing of oxygen in LD Converter


Hot metal pre-treatment to control S and P
Simultaneous blowing of oxygen from top and inert
gas/oxygen through the bottom. Industrially the process is
known as combined blown steelmaking or hybrid blowing
Refractory lining materials and refractory maintenance and
repairing procedures
Usage of ladles to perform refining, degassing, deoxidation
and inclusion engineering
Process control and automation

Present Status of Steel Industry:


Plain carbon steels are produced principally by the following routes:
1) Blast furnace Basic oxygen furnace Ladle treatmentscontinuous castingRolling flat or long
products. Adopted by Integrated Steel Plants
2) Electric Arc Furnace Ladle treatmentsContinuous castingRolling Mostly long products but

occasionally flat products. Adopted by Mini Steel Plants


Alloy and special steels are produced by route 2. Some plants employ Argon-Oxygen-Decarburization process
instead of Electric Arc Furnace
Top steel producers in the world in the year 2010-2011
Rank

Plant

Production (Million (million tons)

ArcelorMittal, Luxembourg

103.3

Nippon Steel, Japan

37.5

Baosteel Group china

35.4

Posco, South Korea

34.7

Tata Steel India

24.4

10

United States Steel Corporation

23.2

20

Sumitomo Steel Industries, Japan

14.1

21

SAIL, India

13.7

Steelmaking in India
The first attempt to revive steel industry in India was made in 1874 when Bengal Iron Works cam into being at
Kulti near Asansol in west Bengal. In 1907 Tata Iron and Steel Company was formed and produced steel in
1908-1909. In 1953 an integrated steel plant in public sector in Rourkela was signed with German Company.
Then more integrated steel plants were added.
Indian steel industry is organised in three sectors as shown in the following:

Integrated
steel plants

Mini steel plants

Induction
furnaces

Public sector

Private Sector

Rourkela

TISCO

Uttam steels

Dispersed

Bhilai

ESSAR

Kalyani steels

In vzrious

Durgapur

ISPAT

Lloyd steel

Parts of the
country

Bokaro

JSW

Usha martin

Salem

Tata Metalics

Alloy steel plant


Durgapur

Mukand ltd.

Indian iron and steel


company

(Reader may add


more).

Visvesyary a iron and


steel
RINL, Vishakhapatnam

Ghosh and A chatterjee: Ironmaking and steelmaking


List of steel producers, wilkepedia
www.steelads.com // largeststeel/TOP30-Worlds- Largest- steel- Companies.html

Lecture 2: Modern steelmaking

The Lecture Contains:

Concept

Concept

The
concept
of
Secondary steelmaking
modern
steelmaki
Continuous casting and thin strip casting
ng is to
make use
Final finishing operations
of the
steelmaki
ng vessels like converter, ladle and tundish of a continuous caster. In all these vessels molten steel is handled
for one or the other purpose. For examples ladles are used to transfer the molten steel either to ingot casting or
continuous casting. Tundish of a continuous caster is used to transfer molten steel to the continuous casting
mould. In all these vessels the residence time of molten steel is sufficiently long so as to carry out some refining
operations like composition adjustment, removal of gases, control of S, removal of inclusions etc. in ladle and
tundish. This has led into the development of ladles, tundishes for some refining operations like deoxidation,
inclusion modification, desulphurization etc. and other operations like composition adjustment, inclusion
removal etc. The basic idea of employing ladles and tundishes for either refining or composition adjustment or
for producing clean steels is to use the steelmaking units like converter and electric furnace for producing steels
without much bothering for final chemistry. Modern steelmaking comprises of hot metal / scrap to finished
products through the following
Primary steelmaking

a) Primary steelmaking
b) Secondary steelmaking
c)Continuous casting
d) Finishing operations

Principle chemical reactions


Hot metal contains
top and the following reactions occur:

and

. Oxygen is blown from

1
2
3
4
5
6
7
Note the following:

No heat is supplied from outside. The heat produced due to chemical reactions is sufficient enough to

raise the temperature of hot metal from around


of
.

to molten steel tapping temperature

Except carbon which is removed as a gaseous phase rest all other elements form slag. Slag formation of
desired chemistry and physico-chemical properties is vital for the successful operation of converter
steelmaking technology.

Typically converter steelmaking technology allows to tap liquid steel in approximately every 50 to 60
minutes with specified steel chemistry and 500-1000ppm dissolved oxygen.

Typically oxygen blowing time is independent of converter capacity i.e.


minutes irrespective of the converter capacity.

is blown for 15 to 20

b Electric Arc furnace (E A F)


In electric arc furnace steelmaking scrap + hot metal + directly reduced iron is used to produce plain carbon
steel
Electric energy is the principle source of thermal energy. Graphite electrodes are used to supply the current (see
figure 2.2). The AC electric arc furnaces are very popular. EAF can be either normal power or ultra high power
(UHP) with single or twin shell, with or without bottom stirring or post combustion. EAF generates a
considerable noise. Now a days EAF has occupied a unique position in the steel industry: EAF can be switched
over easily to produce plain C or alloy steel depending on the market requirements. The details are given in
lectures 15,16 and 17.

Figure 2.2: Electric arc furnace


Secondary steelmaking
The objective of secondary steelmaking is to make the steel of desired chemistry and
cleanliness by performing the following treatments in Ladle:
a) To stir the molten steel by purging inert gas through the bottom of the ladle.
b) To inject slag forming powder either through a lance for further refining
c) To produce clean steel either by removing inclusions or modify them by suitable
injecting materials

d) To carry-out deoxidation and degassing.


Secondary steelmaking in ladles has become an integral part of steelmaking. Ladles have
additional heating facility and are called Ladle furnaces (LF).
There are several practices adopted for degassing, like vacuum tank degasser, stream degassing
and recirculation degassing. In recirculation degassing steel is made to flow from the ladle into
a separate degassing chamber and then returned after exposure to the vacuum. In one of the
recirculation degassing practice metal circulation is achieved by dipping the degassing vessel
into the ladle, the liquid steel is raised into the vessel, degassed and returned into the ladle.
In another practice a refractory lined vessel is equipped with two legs (called snorkels) for
dipping into the ladle containing molten steel. Pressure is reduced and argon gas is passed into
one of the snorkel, thereby molten steel is raised into the vessel and recirculates back into the
ladle through the other snorkel. Details are given in lectures 25 and 26.

Continuous casting and strip casting


Molten steel is being cast continuously in to billets, blooms and slabs depending on the desired product i.e.
whether long or flat products. In continuous casting, tundish, mold and secondary cooling sprays are arranged
such that steel is poured continuously from the tundish and the solidified cast product is withdrawn
continuously.
The arrangement of the tundish, mold and spray is shown in the figure 2.3.

Figure
2.3:

continuous casting process

The original continuous casting machines were of vertical types. Now most of
the continuous casters have either curved mould (Figure 2.3a) or vertical mold
with bending rolls.
In the continuous casting, tundish is the important refractory lined vessel. It
feeds the molten steel into the molds placed beneath the tundish through a
submerged nozzle. Tundish also acts as reservoir of molten steel during ladle
change-over periods and sequence casting. Modern tundishes are equipped with
furniture like dams, weirs, slotted dams etc. to modify the molten steel flowing
in the tundish during the process of continuous casting. Modern developments
include thin slab caster, liquid core reduction. Thin slab casters are connected to
the strip mill. The objective is to integrate the casting and rolling in order to save
reheating cost.
Strip casting is ( Figure 2.3b) also becoming popular in steel plants. Here molten
steel is cast directly into the strip. Lectures 33 and 34 describe the process of
continuous casting.
Final finishing operations:
It has been considered appropriate to include final finishing operations in
steelmaking course to appreciate integration between chemistry and cleanliness
of steel and the final finishing operations. It is thought that the reader can
appreciate the role of steelmaking in the product development and failure. The
following finishing operations are dealt with in lectures 35,36 and 37.

Deformation processing technologies like forging rolling etc.


Heat treatment to produce the finished product. Heat treatment consists of
heating the steel products to a temperature in the austenitic region and
then cooling.
Surface hardening treatment

References:

Chakrabarti: Steel making

Lecture 3: Science base of Steelmaking

The Lecture Contains:


Preamble
Equilibrium between phases
Activity of solution

Preamble

Raoults law

In
steelmaki
ng, the
Interaction parameter
impurities
like
carbon,
silicon, manganese, phosphorus and sulphur are removed from hot metal through a combination of gas/metal,
gas/slag and gas/metal/slag reactions so as to produce steel of desired chemistry and cleanliness (cleanliness
refers to the inclusions). Science of steelmaking involves equilibrium concentration of an impurity between the
phases for a given set of temperature and pressure,and the rate of transfer of an impurity from the hot metal.
Henrys law

Equilibrium between the phases:


The phases in steelmaking are hot metal, molten slag and gas. Hot metal is a multi-component solution in which
impurities like carbon, silicon, manganese, phosphorus and sulphur are dissolved in very low amount (total
concentration of all the impurities is approximately 5% to 6%) in iron. Slag is a solution of predominantly
oxides with small amounts of sulphides, phosphides, silicates etc. Composition of the solutions in steelmaking
is conveniently expressed either as weight% (Wt%) or mole fraction(N). The mole fraction of the ith component
in a solution of n components is
(1)
where is the number of moles of ith component. The equilibrium of a component between the liquid phases is
expressed in terms of integral molar free energy. Integral molar free energy of solution
(2)
represents free energy of solution and
is the free energy of pure components before entering into the
solution. The quantity
is the partial molar free energy of mixing of component i and represent the change of
energy or work which a mole of pure component i can make available.
Chemical potential is a useful concept to describe chemical equilibrium between liquid phases. At chemical
equilibrium the chemical potential of any component is identical in all phases. Knowledge of chemical potential
is important in steelmaking because an impurity can transfer in the gaseous or slag phase only when its
chemical potential is lower than in hot metal.
The criterion for equilibrium at constant temperature and pressure is the change in the integral molar free
energy of the solution,

i.e.

for an infinitesimal process and


for a finite process
Where

is change in integral molar free energy

(3)

At constant temperature and pressure when


chemical reaction say
standard free energy change. At equilibrium

, where K
is equilibrium constant.

, a process occurs spontaneously. For an isothermal


, where J is activity quotient and
is the

(4)

Activity of solution
In dealing with chemical reactions in solution it is important to define the
activity of a component. Activity of a component denotes its effective
concentration. It is related to fugacity as
(5)
is the fugacity of component i in solution and is the fugacity of a
component in its standard state (standard state could be either pure element
or compound at 1 atmospheric pressure) So at standard state activity equals
1. In an ideal gas activity of a component i is equal to its partial pressure.
Raoultss Law
An ideal solution obeys Raoults law, in which activity of a component ai
equals to its mole fraction
(6)
Real solutions exhibit either positive or negative deviation from Raoults law
for a binary solution. Deviation from Raoult law is taken care by activity
coefficient
(7)
The Fe-Mn forms an ideal solution, whereas the Fe-Cu exhibits strong
positive deviation and the Fe-Si strong negative from Raoults law.
Physically it implies that in Fe-Cu solution copper has a strong tendency to
segregate, and in Fe-Si solution silicon has a strong tendency to form
chemical compound with iron.
In binary liquid oxides, FeO-MnO behaves ideally, whereas most binary
silicates i.e.
show negative deviation
from Raoults law.
Henrys law
Liquid steel, and to a reasonable extent hot metal primarily fall in the category of dilute solution. In a dilute
binary solution activity of a solute obeys Henrys law, which is stated as
(8)

where is a constant (activity coefficient for the solute in dilute binary) and is the mole fraction of the
specie i. Solutes in all infinite dilute solutions obey Henrys law. Deviation from Henrys law occurs when the
solute concentration increases.
In steelmaking the concentration of solute in molten steel is expressed in weight percent. It is frequently most
convenient to choose the infinitely dilute solution expressed in terms of weight percent as the standard state.
This is defined as
(9)
For weight percent i other than zero
(10)
Interaction parameter
Molten steel contains several dissolved solutes in dilute scale. For example, molten
steel contains C, S, P, Si, Mn etc. This steel is a multi-component solution. In
multi-component solution solutes interact with one another and thus influence
activities of other solutes. If Fe is the solvent, and 1, 2.k are solutes in dilute
state, then
(11)
The term is known as interaction parameter describing the influence of solute j
on the activity coefficient of solute i. The value of interaction parameter can be
found in any book on thermodynamics.
The concept of interaction parameter is very important in estimating the activity of
a solute element in presence of other solute elements. For example we want to
calculate the activity of sulphur in hot metal of composition C = 4%, Si = 1.5%,
Mn =1% and S = 0.04%
.By assuming infinite dilute solution as the
standard state, the activity of sulphur is given by

Substituting the value of


we get

and
and activity of sulphur is 0.43.

References
A.Ghosh and A. Chatterjee: Ironmaking and steel making
The Lecture Contains:
Preamble

The role of slag in steelmaking


Structure of pure oxides
Structure of pure silica
Network former and breaker oxides
Structure of slag

Preamble
Slag plays a very important role in steelmaking to the extent that it is said that make a slag and slag makes
steel. Slag is a generic name and in steelmaking it is mostly a solution of oxides and sulphides in the molten
state and the multi-crystalline phases in the solid state.
Slag is a separate phase because

It is lighter than molten steel and


It is immiscible in steel

Slag is formed during refining of hot metal in which Si oxidizes to


, Mn to MnO, Fe to FeO, and P
to
, and addition of oxides such as CaO, MgO, iron oxide, and others. The addition of oxides is done to
obtain desired physico-chemical properties of slag like melting point, basicity, viscosity etc. All these oxides
float on the surface of the molten steel. Synthetic slag is also used to absorb inclusions to produce clean steel for
certain applications.
The role of slag in steelmaking:

It acts as a sink for impurities during refining of steel


It controls oxidizing and reducing potential during refining through FeO content. Higher FeO makes the
slag oxidizing and lower FeO reducing
It prevents passage of nitrogen and hydrogen from atmosphere to the molten steel
It absorbs oxide/sulphide inclusions
It acts as a thermal barrier to prevent heat transfer from molten steel to the surrounding.
It protects steel against re-oxidation
It emulsifies hot metal and promotes carbon oxidation.
In electric steelmaking slag prevents the radiation of heat of arc to the walls of the furnace and roof

The above functions require that slag should possess certain physical (density, melting point, viscosity) and
chemical properties (basicity, oxidation potential). Both physical and chemical properties are controlled by
composition and structure of slag. In steelmaking slag is predominantly a mixture of oxides with small amounts
of sulphides and phosphides. The oxides are either acidic or basic in nature. We will first consider the structure
of pure oxides and then we discuss what happens on addition of one type of oxide to the other.
Structure of pure oxides
In pure oxides

Metallic cations are surrounded by oxygen ions in a three dimensional crystalline network

Each cation is surrounded by the maximum number of anions in a closed packed structure, and this
number is called coordination number
Cations of basic oxides such as CaO, MgO, FeO (
etc. have radii smaller than that of
cations of
Structure of an oxide depends on the ratio of radii of cations/anions as shown in the following table

Structure

CN

Cation/anion

Examples

Cubic

1 0.732

Octahedral

0.732 0.414

CaO, MgO, MnO, FeO


etc.

Tetrahedral

0.414 0.225

SiO2, P2O5

Triangular

0.225 0.133

CN = Coordination number
As can be seen in the table the basic oxides have octahedral and acidic oxides tetrahedral structure.

Structure of pure silica


In silica, each atom of silicon is bonded with four oxygen atoms and each atom of oxygen is bonded with two
silicon atoms. The elemental tetrahedral of silica are joined at the vertices to give the hexagonal network in
three dimensions. The structure of pure solid and molten silica is shown in the figure

Figure 4.1: Structure of silica (a) solid and (b) molten

As seen in the figure 4.1a, each tetrahedron is joined at the vertex so as to obtain the three dimensional
hexagonal network. During melting the crystalline network of silica is broken by thermal agitation as shown on
figure 4.1b. Only at very high temperatures, molten silica consists of equal number of
and
ions.

Network former and breaker oxides


It must also be understood that the bonding between cations and anions in acidic oxides like SiO2 and
is
strong, and these simple ions group to form complex ions as
and
. In slags, these tend to form
hexagonal network. These oxides are, therefore, called network formers or acids. These acidic oxides can accept
one or several oxygen ions.
Basic oxides like CaO, MgO,
FeO dissociate and form simple ions like
and . All basic oxides are
donors of oxygen ions. These oxides are called network breakers, since they destroy the hexagonal network of
silica by reacting with it.
Structure of slag
Most slags are silicates. Pure silica has very high viscosity at the melting point. Addition of basic oxides
decreases the viscosity by breaking the hexagonal network of silica. Consider the addition of CaO to molten
silica. Calcium oxide dissociates to

Each mole of CaO introduces one mole of oxygen ions in the hexagonal network of silica and can break two
vertices of the hexagonal structure of silica. By adding 2 moles of
for every mole of silica all the four
vertices are broken and we simply have
and
as shown below

Note that

can combine with two tetrahedrons

The reaction between alkaline base oxides, e.g. Na2O and SiO2 is as follows:
and

Since Na has one charge, each tetrahedron of silica will have Na ion attached to oxygen ion. As a result one
should expect more decrease in viscosity of silica on addition of alkaline base oxides as compared with basic
oxides.

The number of vertices destroyed depends on the fraction of basic oxide, i.e. the ratio of O/Si as shown in the
table
O:Si Formula

Structure

Equivalent silicate ions

2:1 SiO2

All corners of tetrahedron are


shared

(Si6O15)6 or (Si8O20)8

5:2 MO.2SiO2

One broken link per


tetrahedron

(Si3O9)6 or (Si4O12)8

3:2 MO.SiO2

Two broken link


per tetrahedron

(Si3O9)6

7:2 3MO.2SiO2 Three broken link per


tetrahedron

(Si2O7)6

4:1 2MO.SiO2

(SiO4)4

All link are broken

All the four vertices will be broken when 2 moles of CaO are added for each mole of silica. The resulting slag
would consist of
and
ions
References :
L.Coudurier, D.W.Hopkins and I.wilkomirsky: Fundamentals of metallurgical processes
Lecture 5: Physico-chemical properties of slag

The Lecture Contains:


Introduction
Viscosity
Basicity
Oxidation and reduction potential of slag
Slag foaming
Operational advantages

is viscosity,
A is an
empirical
constant, E is
activation
energy, T is temperature and R is gas constant. For a given temperature, addition of basic oxides decreases
rapidly the viscosity of a slag which contains
and
. The decrease in viscosity is greater with alkaline
oxides like
and fluorides like
as compared with CaO and MgO for the reasons discussed in lecture 4.
Quantification of slag foaming

Alumina acts as a network breaker in an acidic slag and network former in a basic slag.
Presence of solid particles in slag increases the viscosity of slag as shown in the following expression:
(2)

Where is volume fraction of solids in slag


If volume fraction of the solid is in between 5% to 10%, viscosity of slag increases by 114% to 130%.

Basicity:
Basicity can be understood either from ionic or from molecular nature of slag. The ionic nature of slag assumes
slag to consist of ions. In slags, acidic oxides can accept one or several
ions, whereas a basic slag is a
donor of
ions. For example, 1 mole of
can accept 2 moles
ions so that each tetrahedron in
hexagonal structure becomes independent of each other. Similarly each mole of
can accept 3 moles of
ions. Thus
(3)

Amphoteric oxides behave as bases in presence of acid or as acids in presence of a base:


(4)

Bases can supply

ions

In a neutral slag enough oxygen ions will be present to ensure that each tetrahedron remains independent of

each other. In binary


, slag will become neutral when CaO is 66.7%, which corresponds to the
formation of
Slag will be basic only when CaO content is more than 66.7%. Basicity can be
expressed in terms
ions which are in excess than that required, thus satisfying the requirements of acidic
oxides. In 100 g of slag
(5)

In industrial practice ionic definition of basicity is not useful; the molecular approach is more useful. The
molecular approach assumes slag to consist of chemical compounds. The basicity of slag is
(6)

In presence of different basic oxides, the different strength of the basic oxides should be considered. In a slag
which contains CaO, MgO,
and
, the basicity is
(7)

In slag/metal reactions which involve desulphurization and dephosphorization, the concept of free lime in slag
is useful. Free lime in CaO,
and
slag is that amount which is available after the formation of neutral
compound like 2CaO.
, 3CaO.
(8)
For 100 ton hot metal with 1% silicon and 0.2% P the calculation shows that free CaO in slag would be
available when CaO content exceeds 4540Kg.
Oxidation and reduction potential of slag
It refers to the capability of slag to transfer oxygen to and from the molten steel bath. FeO content of slag
determines the oxidation potential of slag. Thus activity of FeO in slag is an important parameter. The
equilibrium between FeO of slag and oxygen of steel is

(9)

The activity of oxygen in metal is proportional to the activity of FeO in slag.

Slag foaming:
Foam is a dispersion of gas bubbles in a liquid. A liquid is said to be foaming when gas bubbles could not
escape through the liquid and as a result height of the liquid increases. In steelmaking, slag foaming can occur
due to the following reactions:

This reaction occurs within the slag. The other reaction

This reaction occurs at the gas/metal interface. In both the cases when the CO gas bubbles are unable to escape
through the slag, the slag is said to be foaming. If the reaction between carbon and oxygen occurs deep into the
bath i.e. reaction 2 then gas bubbles have enough time to grow in size and can easily escape through the slag
layer as compared to when the gas bubbles are produced by reaction 2. The reaction 2 occurs within the slag
Is slag foaming desirable? Yes to the extent that slag should not flow out of the reactor. Slag foaming enhances
the reaction area. In electric steelmaking foamy slag practice prevents the transfer of heat of the arch to the
refractory lining.
Operational advantages: A foaming slag

Shields molten steel against atmospheric oxidation


Acts as a thermal barrier to prevent heat losses
Shields the refractory lining particularly in electric arc furnace
Control heat transfer from the post combustion flame
Quantification of slag foaming:
Foaming index = Foam layer thickness/ average gas velocity
Low foaming index means easy escape of gas bubbles which can be obtained either by smaller gas
bubbles or higher gas velocities. Foam life is directly proportional to foaming index
Increase in slag viscosity increases foaming index. Presence of solid particles and surface active agents
increases the foaming index. Addition of calcium fluoride decreases the foaming index by decreasing
the viscosity of slag. Foaming index (FI) can be calculated from the physical properties of slag and size
of the gas bubble:
(10)

Calculate the foaming index slag of composition

and 5%

at 1773 K slag from

the following data:


and
Substituting the value of the variables in eq. 10 we get
for

and 0.01m.

and 485 for

If the volume fraction of solid particles in slag is 0.1


s for

and 631 s for

Note that foaming index increases to 1.3 times due to presence of solid particles in slag.
Consider a slag of composition
and

and 1% Ca F2 at 1873 K whose


and

This slag would have foaming index 9s. Foaming tendency decreases drastically due to production of
Ca F2 in slag.
Reference to lectures 3 and 4
A.Ghosh and A.Chatterjee:: Ironmaking and steelmaking
Zhang and Fruehan: Metallurgical and Materials Trans. B, 26(8), 1995

Lecture 6: Steel Making Reactions: Oxidation of Iron and Silicon

The Lecture Contains:


Introduction
What are oxidation reactions?
Iron oxidation
Oxidation of silicon

Introduction
In steelmaking the impurities in hot metal like carbon, silicon, manganese, phosphorus and sulphur
are removed through oxidation and slag formation so as to produce steel of desired chemistry and
cleanliness. For this purpose oxygen is supplied and slag of desired chemistry is formed. When
oxygen is supplied, oxidation of all impurities of hot metal including iron begins simultaneously.
To understand the conditions favourable for the removal of an impurity, we will first consider
oxidation of an individual impurity. We will be using principles of thermodynamics to obtain the

optimum conditions for the removal of an impurity. Note the following

Carbon can oxidize to CO and CO2 but at high temperature carbon oxidation to CO is highly
probable. We will consider oxidation of C to CO.

In expressing activity of solutes in molten steel, Henrys law is used by using 1 weight %
standard state. Raoults law is used to express activity of solutes in slag.

Since impurities are dissolved in molten metal, reactions between impurity and oxygen occur
with dissolved oxygen.

Square brackets [ ] in a reaction denote impurity in metal, round brackets () in slag and
curly {} in gas.

What are the oxidation reactions?


The principle reactions in steelmaking comprise of oxidation of impurity elements by oxygen dissolved in hot
metal or FeO content of slag.
(1)
(2)
(3)
(4)
(5)

All reactions are exothermic.


C is removed as gas.
Except C, all other impurities are removed as oxides and all these oxides float on the surface of the
molten metal during refining of hot metal to steel.
Iron oxidation is unavoidable. Oxidation of Fe is loss in productivity; hence its oxidation must be
controlled.
Oxygen must be dissolved to remove an impurity from the hot metal.

We begin with considering oxidation of an individual element and evolve the optimum conditions using
thermodynamic principles.

Iron Oxidation:
Oxidation of iron i.e. reaction 1 is the most important since it controls

FeO content of slag and oxygen content of steel


Loss of iron in slag and hence affects productivity
Oxidation potential of slag

In addition to the above FeO also helps in dissolution of lime in slag.


Consider the reaction

The equilibrium constant

is
(6)

h is henrian and a is raoultian activity. Since Fe in steel is pure;


and

,
(7)
(8)

In equation 8, T is in K. By equations 6, 7 and 8 we get


(9)

The equation 9 can be used to determine wt% O in steel at any temperature T, when
in slag is known.
When pure FeO is in contact with Fe;
. We can determine
at saturation for different
temperatures:

T (K)
1873

0.233

1923

0.285

We note that increase in temperature increases oxygen dissolved in molten iron.


The above values of dissolved oxygen correspond when pure FeO is in contact with Fe pure. In steelmaking
FeO is present along with other oxides like calcium oxide, magnesium oxide, silica, manganese oxide etc, hence
activity of FeO is influenced by other solute oxides. Thus
where
is activity coefficient and
mole fraction of FeO in slag,.
depends on slag composition. In
CaO-FeO system, as
ratio increases
increases; physically it means that CaO replaces FeO
from FeO.
. The following expression is used to express
:
(10)

Consider a slag with


= 0.5 ;
calculated by equation 9.

according to equation 10 is 0.31; [wt% O] in steel would be 0.072 as

Few other equations are available; i.e.


(11)
(12)
The calculations are made on [wt% O] by equations 9, 11 and 12 at different temperatures using
.

T (K)
1873

0.233

0.229

0.220

1923

0.285

0.280

0.268

There is a slight difference in the values of dissolved oxygen content in steel. But all equations suggest that
increase in temperature increases dissolved oxygen in iron which is in contact with pure FeO. This calculation
indicates that control of temperature is important to limit the dissolution of oxygen in molten iron.

Oxidation of Silicon:
Consider reaction 2

(13)
(14)
Different sources give the following expression for
(15)

(16)

Both equations predict that decrease in temperature increases


Equation 15 predicts 15-17% higher
than equation 16.

. There is a slight difference in values of

Conditions favourable for silicon oxidation are

Low temperature

Low

in slag. A basic slag favours silicon oxidation.

In a basic slag, silicon oxidation occurs practically to a very low value since
decreases activity of silica in slag.

reacts with CaO and

Another important feature of silicon reaction is very high affinity of silicon with oxygen, silicon can be used
as a deoxidizing agent.
By equation 14
(17)

by equation 16 and using

, we get
(18)

Equation 18 shows drastic reduction in oxygen content of steel due to addition of silicon. This suggests that
silicon is a very effective deoxidizer. Normally silicon is used as ferrosilicon in steelmaking.
Reference

A. Ghosh and A. Chatterjee; Ironmaking and steelmaking


R. Tupkary et.al. Modern methods of steelmaking
A.K.Chakrabarti: Steelmaking

Lecture 7: Oxidation of Manganese and Carbon

The Lecture Contains:


Behaviour of manganese
Oxidation of manganese
Reduction of manganese
Oxidation of carbon
Rimming reaction

Illustration
Behavoiu
r of
manganese in iron-carbon melt:

Mn is soluble in iron in any proportion


Mn forms ideal solutions in iron
Carbon lowers the activity of Mn in Fe-Mn-C system by forming

Oxidation of Manganese:
Mn is oxidized readily at relatively low temperatures and can form oxides like
MnO is stable at high temperature.

etc. But

(1)
(2)
The reaction 1 occurs with dissolved oxygen in metal, whereas reaction 2 is a slag/metal reaction. Both
reactions are exothermic. Lower temperature favours oxidation of Mn from metal to slag; whereas higher
temperature favours reduction of MnO of slag and there occurs reversal of Mn into steel. Reduction of MnO in
slag is important; we consider reaction 2
(3)
Replacing activity by mole fraction and using

, we get,
(4)

Grouping all activity coefficient terms and putting


We get,
(5)
Where is an equilibrium quotient and it depends on composition of slag. Distribution of Mn between slag and
metal can be written as
(6)
(7)
According to equation 7 increases with decrease in temperature(
1923K, 1873K and 1773K respectively)
Condition for oxidation of Mn according to equation 6

and 20.33 at temperatures

High activity of
in slag which means an oxidizing slag
Decrease in temperature increases K* according to equation 7.

Reduction of Mn in slag
Conditions for reduction of MnO, that is reversal of reaction 2 is important. The reduction of MnO in slag
transfers Mn from slag to metal and increases the concentration of manganese. The following are the
conditions for the reduction of MnO in slag

Low activity of FeO in slag which means a reducing slag


High temperature which decreases

Illustration:
Consider a slag of basicity 1.8. At this basicity the activity coefficient of MnO in slag is 1.6. The mole
fraction of FeO and MnO in slag is 0.25 and 0.05 respectively. Determine the equilibrium content of Mn and
O in steel at 1873K. Given

Using equilibrium constant definition, we can write


(8)

Substituting the values, we get at 1873K

Using equations 10 of lecture 6

We get
Hence

Calculations performed at 1773K shows that [wt% Mn] is 0.032. This means that decrease in temperature
favours removal of manganese from metal to slag. The reader may perform calculations at 1973K and
interpret the calculations.
Oxidation of Carbon
It is important to note that amongst all steelmaking reactions, oxidation of carbon is the reaction whose product
is gas i.e. CO. Therefore this reaction is of very much significance during steelmaking because

CO gas during escape from the molten bath can induce stirring in metal and slag phases during
steelmaking.
CO gas can cause slag to foam which leads to increase in surface area.
CO gas has a high calorific value and combustion of CO in steelmaking can contribute to energy
efficiency.

Carbon oxidation is also known as decarburizing reaction


(9)
(10)
(11)
If we assume

that is at low concentration of carbon and oxygen in molten metal then


(12)

According to eq. 12, the product


at a given temperature depends only on partial pressure of
CO in equilibrium with melt. It is important to note that
depends on the location of nucleation of CO in steel
melt. If CO nucleates deep into the bath then
will be great
Let us calculate equilibrium content of carbon and oxygen at 1873K for
The value of
is calculated from

[wt% C]

1.2 atm and 1.5 atm

[wt% O ]

0.05

0.0405

0.0486

0.0608

0.1

0.0202

0.0242

0.0303

0.5

0.0040

0.0048

0.0060

1.0

0.0020

0.0024

0.0030

From the table we note that

Decrease in carbon content increases the oxygen dissolved in steel. This is important in connection with
production or ultra low carbon steel for certain applications. Production of ultra low carbon steels will
be accompanied with dissolved oxygen if precautions are not taken during steelmaking.
Increase in
increases [wt% O] in steel

er than atmospheric pressure.

Let us consider the evolution of CO gas. According to equation 9,


12 Kg C produces 22.4

CO (1 atm and 273K)

1 Kg C produces 1.87

CO (1 atm and 273K) which is equivalent to 12.83

CO (1 atm and 1873 K)

Now for 1000 Kg hot metal and 0.2% carbon in steel


CO production would be 488
(1atm, 1873 K) / ton of hot metal. This volume of CO will evolve no doubt
over a period of time but at any time large amount of CO will be escaping the system. Escaping of this gas
will agitate the bath and contribute to enhanced rates of mass transfer reactions. Also care must be taken for
the easy and unhindered escape of CO gas from the vessel failing which foaming and eventually expulsion of
slag may occur.
Rimming reaction
Other aspect of carbon reaction is the evolution of CO during solidification of steel. As the temperature of
molten steel decreases from 1873K to 1773K,
increases from 494 to 532 which results in decrease
in
as steel cools. This will lead to CO evolution during solidification and is called
rimming reaction. Rimming reaction induces stirring in the solidifying liquid steel and minimizes segregation
of solutes.
Reference

A. Ghosh and A. Chatterjee; Ironmaking and steelmaking


R. Tupkary et.al. Modern methods of steelmaking
A.K.Chakrabarti: Steelmaking

The Lecture Contains:


Preamble
Equilibrium considerations
How low

should be?

Effect of FeO and CaO on dephosphorization


Illustration
Conditions for dephosphorization
Conditions for simultaneous removal of C and P

Preamble:
Phosphorus removal from hot metal is the most important refining reaction.
Phosphorus has
atomic number 15 and it can give up all 5 electrons from its outermost shell to
become
or accept 3 electrons to become
to attain stable configuration.
This means that phosphorus can be removed both under oxidizing as well as
reducing conditions.But removal of phosphorus under reducing conditions is not
practical since its removal is highly hazardous. Thus P removal is practised mostly
under oxidizing conditions..
Equilibrium Considerations:
Phosphorus removal reaction
(1)

At T > 1382K,

becomes positive which results in decomposition of

P and O.Thus removal of phosphrous requires that

to

must be reduced.

(2)
Now
and

(3)
(4)

By equation 2 and 3 and replacing

by using Raoults Law and after rearrangement

(5)
is activity coefficient of
in slag. The LHS of equation 5 is index of
dephosphorization and denotes distribution of phosphorus between slag and
metal. Higher value of LHS demands low

How low

in a slag of a given composition.

should be?:

Consider dephosphorization in a slag of


in slag = 0.01. Let us calculate

at 1773K. Initial %P in metal is 0.1 and mole fraction of


which will allow dephosphorization.

(6)
At 1773 K,
can be determined by equation 3 and 4. We substitute the values in equation 5. We
get

. Now the question before us is how to attain such a low value of

in a slag of

given composition? Such a low value of


can be attained when we use basic oxides which have a very
strong tendency to form a stable chemical compound. The different basic oxides have different ability to lower
. The following expression describes the relative effects of basic oxides on

(7)
Alkaline oxides
not used.

and BaO are stronger than CaO but they are corrosive to the refractory lining and hence

Consider a slag
We calculate

at different temperatures
T (K)
1773
1823
1873

Decrease in temperature increases

which favours dephosphorization reaction.

Effect of FeO and CaO on dephosphorization:


Figure 8.1 shows the variation of dephosphorization index
as a function of wt%FeO for
CaO-FeOslag at different basicities. The dephosphorization ratio increases with

Figure 8.1:

Dephosphorization index as a function of weight


percent FeO content of slag for different basicities.

increase in FeO content of slag and becomes maximum in between 15-16% FeO at all basicities. Further
increase in FeO beyond 15-16%, dephosphorization decreases. The above behaviour can be observed at all
basicities of slag.
The above behaviour is due to the dual role of FeO. FeO is the source of oxygen for oxidation of P according to
the following reaction
(8)

For a given basicity of slag, as FeO content of slag increases oxidizing power of slag increases and phosphorus
oxidation according to reaction 8 will be favoured because CaO of slag decreases the activity of
by
forming a stable compound. Beyond the optimum value of FeO in slag FeO replaces CaO and may either
combine with CaO or with
. FeO is a weak base compared with CaO as a result of which the
dephosphorization ratio decreases with addition of FeO beyond an optimum value.
The maximum dephosphorization ratio increases with the increase in the basicity of slag as can be seen in the
figure 7.1. Higher basicity requires higher amount of CaO dissolved in slag. Any undissolved CaO will not be
effective for dephosphorization. Optimum value of FeO is more or less independent of the basicity of slag. Thus
control of FeO in slag is important for efficient dephhosphorization.
Conditions for dephosphorization:
Dephosphorization requires oxidizing and basic slag:
(9)
(10)
(11)

in slag should be high. This means slag should have free dissolved lime.
High basicity of slag is required.
in slag should be high; slag should be oxidizing. However for efficient
dephosphorization the FeO content of slag should be in between 15 to 16%.

Low temperature favours high


Conditions for simultaneous removal of C and P
Removal of C and P both require oxidizing conditions but P removal is possible only when a basic and limy
slag is formed. Consider the following reactions occurring simultaneously
(12)
(13)
(14)
(15)
It is assumed in eq. 14 and 15 that henrian activity is equal to (wt %). Both reactions
12 and 13 require oxygen but reaction 13 requires a slag which is basic in nature
in addition to oxygen. Thus, if carbon and phosphorus are to be removed
simulataneously,
an important requirement is the availability of slag which acts as a sink for (
).
Thermodynamically slag is required in which activity coefficient of
is very
low.
The question is how low activity of
should be?. This value can be determined
by
equations 14 and 15 Replacing [wt% O] in equation 14 and 15, and after
rearrangement,
(16)

From equation 16 one can determine the value of activity coefficient of


can lead to simultaneous removal of carbon and phosphorus.

which

Let us calculate the


when molten metal contains 2% C and 0.15% P and
temperature T=1773K. The mole fraction of
in slag is 0.1.
(17)
We can calculate

and

from equations 15 and 17. Substituting all the values

into equation 16 we get


. We can also calculate
The results are given below

at temperatures 1673K and 1873K.

T(K)
1673
1773
1873

The calculations show:

Both decarburization and dephosphorization are possible simultaneously in presence of slag in


which

has extremely low value.

Low temperature requires


in slag to be higher than at high temperature.
Thus low temperature is favourable.

References

A. Ghosh and A. Chatterjee; Ironmaking and steelmaking


R. Tupkary et.al. Modern methods of steelmaking
A.K.Chakrabarti: Steelmaking

Lecture 9: Refractory Materials

The Lecture Contains:


Role of refractory
What is a refractory?
Why required?
Refractory requirements
Melting point of some pure compounds used to manufacture refractory
Properties required in a refractory
Types of refractory materials
Insulating materials

Role of refractory
Refractory materials have a crucial impact on the cost and quality of steel products. The diversification on steel
products and their cleanliness requirement in recent years have increased the demand for high quality
refractory. Steelmaking requires high temperatures of the order of 1600 degree centigrade. In addition
steelmaking handles high temperature phases like molten steel, slag and hot gases. These phases are chemically
reactive; refractory materials are required to produces steels. High quality refractory at a cheaper cost is the
main requirement because cost of refractory adds into the cost of product.
What is a refractory?
Refractories are inorganic nonmetallic material which can withstand high temperature without undergoing
physico chemical changes while remaining in contact with molten slag, metal and gases. It is necessary to
produce range of refractory materials with different properties to meet range of processing conditions.
The refractory range incorporates fired, chemically and carbon bonded materials that are made in different
combinations and shapes for diversified applications.

Why required?

To minimize heat losses from the reaction chamber


To allow thermal energy dependent conversion of chemically reactive reactants into products because
metallic vessels are not suitable.

In steelmaking, the physico- chemical properties of the following phases are important:
Slag: Mixture of acidic and basic inorganic oxides like
temperature
varies in between
.

etc.;

Molten steel: Iron containing carbon, silicon, manganese, phosphorous, tramp elements, non
metallic
inclusions, dissolved gases like nitrogen, oxygen and hydrogen and different
alloying
elements like
etc.; temperature
Gases:

containing solidparticles of
.

etc.; temperature

The above phases are continuously and constantly in contact with each other and are in turbulent motion
Compounds

Melting point

MgO (pure sintered)

2800

CaO(limit)

2571

Si C pure

2248

MgO (90-95%)

2193

Cr2O3

2138

Al2O3(pure sintered)

2050

Fireclay

1871

SiO2

1715

Kaolin (Al2O3. SiO2)

1816

Chromite (FeO. Cr2O3)

2182

Properties required in a refractory


The diversified applications of refractory materials in several different types of industries require diversified
properties to meet the physico-chemical and thermal requirements of different phases. In some industrial units
more than one phase are present e.g. in steel-making vessels slag /metal /gases are simultaneously present in
the vessel at high temperatures. In the heat treating furnaces solid/reducing or oxidizing gases are
simultaneously present. Below are briefly described the properties of the refractory materials:
Refractoriness
Refractoriness is a property at which a refractory will deform under its own load. The refractoriness is
indicated by PCE (Pyrometric cone equivalent). It should be higher than the application temperatures.
Refractoriness decreases when refractory is under load. Therefore more important is refractoriness under load
(RUL) rather than refractoriness.

Porosity and Slag permeability


Porosity affects chemical attack by molten slag, metal and gases. Decrease in porosity increases strength and
thermal Conductivity.
Strength
It is the resistance of the refractory to compressive loads, tension and shear stresses.In taller furnaces, the
refractory has to support a heavy load; hence strength under the combined effect of temperature and load, i.e.
refractoriness under load is important.
Specific gravity
Specific gravity of the refractory is important to consider the weight of a brick. Cost of bricks of higher specific
gravity is more that of lower specific gravity. But strength of bricks of higher specific gravity is greater than
one with lower specific gravity.

Spalling
Spalling relates to fracture of refractory brick which may occur due to the following reasons:

A temperature gradient in the brick which is caused by sudden heating or cooling.

Compression in a structure of refractory due to expansion

Variation in coefficient of thermal expansion between the surface layer and the body of the brick

Variation in coefficient of thermal expansion between the surface layer and the body of the brick is due
to slag penetration or due to structural change.

On sudden heating

On sudden cooling

Permanent Linear change (PLC) on reheating


In materials certain permanent changes occur during heating and these changes may be due to

Change in the allotropic form


Chemical reaction
Liquid phase formative
Sintering reactions

These changes determine the volume stability and expansion and shrinkage of the refractory at high
temperatures.
Thermal conductivity
Thermal conductivity of the bricks determines heat losses. Increase in porosity decreases thermal conductivity
but at the same time decreases strength also.
Bulk density:
Decrease in bulk density increases volume stability, heat capacity.

Types of refractory materials


This can be discussed in several ways, for example chemical composition of refractory or use of refractory or
method of manufacture or in terms of physical shape. Below is given type of refractory depending on its
chemical composition and physical shape.

A) Chemical composition
Refractories are composed of either single or multi-component in organic compounds with non metallic
elements.
Acid refractory
The main raw materials used are
and alumino- silicate. They are used where slag and atmosphere are
acidic. They cannot be used under basic conditions. Typical refractories are fireclay, quartz and silica.
Basic refractory
Raw materials used are
dolomite and chrome-magnesite. Basic refractories are produced from a
composition of dead burnt magnesite, dolomite, chrome ore.
a) Magnesite: Chrome combinations have good resistance to chemical action of basic slag
and
mechanical strength and volume stability at high temperatures.
b) Magnesite: Carbon refractory with varying amount of carbon has excellent resistance to
chemical
attack by steelmaking slags.
c) Chromite- Magnesite refractory: used in inner lining of BOF and side walls of soaking pits.(
basic
refractory)
d) Magnesite: Basic refractory in nature. Magnesite bricks cannot resist thermal stock, loose strength
high temperature and are not resistant to abrasion.

at

Neutral refractory
Neutral refractory is chemically stable to both acids and bases. They are manufactured from
carbon.

and

For details readers may see the references given at the end of lecture 10.

B) Physical form
Broadly speaking refractory materials are either bricks or monolithic.
Shaped refractories are in the form the bricks of some standard dimensions. These refractories are machine
pressed and have uniform properties. Special shapes with required dimensions are hand molded and are used for
particular kilns and furnaces. Different types are:
1. Ramming refractory material is in loose dry form with graded particle size. They are mixed with water
for use. Wet ramming masses are used immediately on opening.
2. Castables refractory materials contain binder such as aluminate cement which imparts hydraulic setting
properties when mixed with water. These materials are installed by casting and are also known as
refractory concretes.

3. Mortars are finely ground refractory materials, which become plastic when mixed with water. These are
used to fill the gap created by a deformed shell, and to make wall gas tight to prevent slag penetration.
Bricks are joined with mortars to provide a structure.
4. Plastic refractories are packed in moisture proof packing and pickings are opened at the time of use.
Plastic refractories have high resistance to corrosion.
Monolithic refractories
Monolithic refractories are replacing conventional brick refractories in steelmaking and other metal extraction
industries. Monolithic refractories are loose materials which can be used to form joint free lining. The main
advantages of monolithic linings are

Grater volume stability


Better spalling tendency
Elimination of joint compared with brick lining
Can be installed in hot standby mode
Transportion is easier

Monolithic refractories can be installed by casting, spraying etc.


Ramming masses are used mostly in cold condition so that desired shapes can be obtained with accuracy.

Insulating materials
The role of insulating materials is to minimize heat losses from the high temperature reactors. These materials
have low thermal conductivity while their heat capacity depends on the bulk density and specific heat.
Insulating materials are porous in structure; excessive heat affects all insulating materials. Choice of insulating
materials would depend upon its effectiveness to resist heat conductivity and upon temperature. High alumina
with thermal conductivity
as insulating materials.

and silica with thermal conductivity

etc are amongst others, used

Ceramic fibres are important insulating materials and are produced from molten silica, titania, Zirconia etc in
the form of wool, short fibres and long fibres. They have excellent insulation efficiency. They are long
weight.
References:
O.P.Gupta: Fuels, Furnace and refractory

Lecture 10: Refractory in steelmaking

The Lecture Contains:


Preamble
BOF refractories

Refractory for secondary steelmaking


Refractory for continuous casting
Refractory for circulation degassing
Refractory for high temperature furnaces
Emerging trends
Refractory maintenance
Future issues
Preamble
In steelmaking, refractory materials are used in converter, electric furnace, ladle, tundish, and reheating
furnaces. In converter, electric furnace, ladle and tundish, molten steel is in contact with slag, whereas in
reheating furnaces steel in the solid form is reheated for deformation processing, heat treatment and surface
hardening methods.
BOF Refractories
Converter is lined with a permanent lining and above it there is a wear lining. Permanent lining thickness may
vary from 100mm to 120mm and is made of chrome-magnesite permanent lining which is given on the full
height of the converter.
Above the permanent lining, wear lining is constructed. The cylindrical portion of the converter (barrel) is lined
with the ramming mass of tar dolomite and tar dolomite bricks. The detachable bottom is constructed by using
mica, fireclay, chrome-magnesite and Mag-chrome bricks.
refractory materials with 15% high purity graphite have been found to provide increased
corrosion resistance.
In duplex blowing (hybrid blowing or combined blowing)
bricks are commonly employed for the
bottom tuyeres and around them, since these areas severely worn.
The slag and metal penetration between the refractory grains, chemical attack by slag, mechanical erosion by
molten steel movement contribute to the wear of the lining materials.
Some developments to counteract this lining wear are

to

i) Dolomite
is added to create a slag of about
saturation level of slag.

which is close

in

ii) Critical wear zones (impact and top pads, slag tapping and trunion areas) are lined
furnaces with high quality bricks.
iii) Slag splashing in which the residual slag is splashed by high speed

has resulted

into

high lining life (refer lecture 14)

iv) Lowering
levels in slag and shorter oxygen-off to charge intervals have
reduced
refractory wear.
Refractory for secondary steelmaking
There are many operation and process in secondary steelmaking like vacuum degassing, ladle refining etc.
Refractories are used in unique combinations of various bricks to meet diversified requirements. Following
condition may be noted:
i) High temperature and long holding times of steel in ladle.
ii) Wide variation in slag composition
iii) Many types of vacuum treatment.
iv) Large thermal changes.
v) Molten steel agitation causes attack by motion of liquid steel.
In all ladle refining processes such as ladle furnace, ASE-SKF, VAD process,
bricks are used at areas,
where slag is in contact with steel. For general wall, high alumina bricks are widely used. For bottom zircon
bricks are used to prevent molten steel penetration into brick joint. In certain cases
bricks
and castables are used in impact areas.
bricks with addition of a couple of metals provides high hot
strength, and are excellent in oxidation resistance.
Refractory for continuous casting
Tundish is a refractory lined vessel in continuous casting. It contains molten steel with minimum heat losses.
Selection of refractory is critical due to longer casting sequence, faster tundish turnaround, higher campaign life
and cleanliness of steel. Fireclay bricks are used. High alumina bricks are considered to be good for tundish hot
rotation. Basic coating material is used over the lining. The coating installation method is gunning. Typically
mixture is used as a coating material.
Tundishes are equipped with dams and weirs. There are made of

boards or alumina bricks.

Molten steel from tundish to mold is fed by nozzle submerged into molten steel in mold. Submerged nozzles
must be resistant to corrosion and spalling, nozzle clogging is also important. Isostatic pressed submerged
nozzle with alumina- graphite-fused silica are being used.
In recirculation degassing steel is made to flow from the ladle into a separate degassing chamber. In RH
process, a refractory lined vessel equipped with two legs (snorkels) is used. These snorkels are immersed into
molten steel. The refractory materials must have adequate spalling and abrasion resistance, volume stability and
corrosion resistance at high temperature and in vacuum. Direct bonded magnesia- chrome bricks, semi rebonded
magnesia chrome bricks are used in the lower vessel and snorkels. Extra high temperature burned magnesia
chrome bricks posses excellent corrosion and abrasion resistance and are preferred lining material.

Refractory lining for high temperature furnaces

Furnaces are used for heating steel within the temperature range
to
for heat treatment and
deformation processing. Many different types of furnaces are used namely soaking pits (batch type) and
continuous furnaces. Fireclay and high alumina refractories are used. Most of the continuous furnaces are lined
with fireclay bricks. Plastic chrome ore ramming mixture and hard burnt chrome magnesite bricks are used to
line the hearth to provide resistance to scale.

Emerging trends
Refractory has undergone many changes to meet the diversified requirements of the industry particularly steel
industry. The main objective is to increase the lining life at reduced cost by developing

High quality refractory for critical applications in steel making at e.g. slag line, impact area of molten
steel stream, bottom tuyere refractory in hybrid blowing, immersion nozzles in continuous casting etc.
In this connection mention may be made of some refractory like MgO-C, Al2O3 Si C C, MgO
Ca O C, Al,Mg and Al-Si alloy stabilized MgO C brick, zircon based refractory, and Al2O3 C

Repairing methods like slag splashing, slag coating, hot patching, gunning (flame gunning involves
melting and spraying on hot surface).

Monolithic refractory

Monolithic refractory
Monolithic linings are a relatively recent development and consist of unshaped refractory products. These are
materials which are installed in some form of suspension that ultimately hardens to form a solid mass. There are
two basic types of monolithic lining, namely castable refractory and plastic refractory
Castable refractory consists of mixtures of coarse and fine refractory grains together with a bonding agent
which is normally based on high alumina cement. Installation of the refractory is important. Due to relatively
poor strength, durability of monolithic lining depends on the design and installation of the anchors.
Monolithic linings are installed by casting the refractory in a mould or by spraying the furnace shell. Largest
problem with use of monolithic refractories are:

Long drying time


Steam explosion.

Furnace refractory maintenance


The following methods are commonly practiced.

Slag splashing
Slag splashing is done in steelmaking vessels. After steel tapping, some amount of slag is retained. Composition
of slag with respect to FeO and MgO is adjusted. FeO makes the slag adhesive on the lining and MgO makes
the lining high temperature resistant. Nitrogen is blown from top to splash the slag. The splashed slag gets
coated on the lining. To reduce excessive slag build up in the bottom, excess slag is then poured before
charging.

In case of hybrid blowing practice formation of skull may result in a failure of the bottom stirring elements.

Slag coating and slag washing


The small amount of liquid slag is retained in the vessel after tapping. Slag is enriched with dolomite or raw
dolomite to cool the slag and to increase its adhesive properties. Vessel is rocked several times to coat the
bottom and bottom joint with a slag.
Hot patching
Self flowing refractory mixtures enable precise maintenance of the scrap impact zone, tapping pad and bottom
joint.
Gunning
By gunning, i.e. maintenance of pre- worn areas with special gunning mixtures, vessel lining life can be
extended.
Flame gunning involves simultaneous melting of a refractory powder and gunning at the hot surface. Since the
gunned repair material is dense and fused directly on the hot surface excellent results on life of lining is
obtained in LD converter.
Future issues of Refractory technology
a)

Durability of refractory for pairing nozzles and side dams determines the success of

b) Technology of mass melting of scrap in converter by using post combustion requires


temperature refractories.
c)

strip casting.
super- high

Super fine powder processing technology to produce refractory.

d) Use of monolithic refractory in steel making and refining furnaces require automating
intelligent repair.
e)

Nano tech refractory is thermal shock and corrosion resistant The nano-particles act

brick lying and

in two ways

They consist of mono spheres and improve properties like elasticity and strength
Control of molecular structure as the particles have many small pores of several hundred
nanometers.

Reference:
P.Mullinger and B. Jenkins: Industrial and process furnaces
Kenneth C. Mills et.al.: A review of slag splashing, ISIJ Intern. 45(2005), No. 5, PP 619-633
Y.Naruse: Trends of steelmaking refractories