Alternative to Fluorspar as a Fluxing Agent in Ladle

Furnace during Secondary Steel Refining Process

Submitted in partial fulfilment of the requirements for the degree of

Bachelors of Technology & Masters of Technology

By
Prashant Choudhary
(Roll No. 14D110020)

Supervisor
Prof. Somnath Basu

Co-Supervisor
Prof. Manish Pande

Department of Metallurgical Engineering and Materials Science

INDIAN INSTITUTE OF TECHNOLOGY BOMBAY

(2019)
i
 Dissertation Approval
The dissertation entitled “Alternative to Fluorspar as a fluxing agent in ladle furnace during
secondary steel refining process” by Mr. Prashant Choudhary is approved for the Dual
Degree of Bachelor of Technology in Metallurgical Engineering and Materials Science and
Master of Technology in Metallurgical Process Engineering.

___________________
Guide

___________________
Co-Guide

___________________
Chairperson

___________________
Examiner

___________________
Examiner

Date: _______________

ii
 Declaration

I declare that this written submission represents my ideas in my own words and where others
ideas or words have been included, I have adequately cited and referenced the original sources.
I also declare that I have adhered to all principles of academic honesty and integrity and have not
misrepresented or fabricated or falsified any idea/data/fact/source in my submission. I
understand that any violation of the above will be cause for disciplinary action by the Institute
and can also evoke penal action from the sources, which have thus not been properly cited, or
from whom proper permission has not been taken when needed.

________________________
(Signature)
Prashant Choudhary
14D110020

Date: ____________

iii
 Acknowledgement

I am very much indebted to all those people who have been there as a source of guidance and
support. First and foremost I would like to express my gratitude to my guide Prof. Somnath Basu
for giving me this project which has a lot more to explore and letting me to find solutions myself
which helped me to grow and understand the subject. I would also thank my co guide Prof.
Manish Pande for guiding me through the experimental procedures. I deeply thank Mr. Amit
Joshi for helping in the Ferrous Process Laboratory for helping me in the experiments. I would
also thank Mr. Jadhav, Mr. Manjhi and other lab assistants in the process. I am thankful to SAIF,
IIT Bombay, for instrumentation.

Prashant Choudhary
14D110020
MEMS, IIT Bombay

iv
 Abstract

Secondary steelmaking process is done to finalize the composition of the steel produced after
the primary steelmaking, which includes chemical composition adjustment of various elements
like Oxygen, Sulphur, Phosphorous, Carbon etc. Ladle furnace, used for the secondary
steelmaking process where for the refining of steel, Use of fluorspar (CaF2) as one of the fluxing
constituent besides Calcium oxide and other oxides. The main purpose of this process is to reduce
the liquidus temperature of the slag generated while maintaining the desired properties of steel
produced. This slag has adverse effect on refractory walls and causes environmental hazards.
Fluxes without fluorspar content is desired which is achieved in some steelmaking process.
Binary, Ternary and Quaternary slag with components CaO, SiO2, Al2O3, MgO are studied by
varying their compositions in order to get the lower liquidus temperature.

v
Table of Contents
Declaration ......................................................................................................................................iii
Acknowledgement .......................................................................................................................... iv
Abstract ............................................................................................................................................v
List of Figures .................................................................................................................... viii
List of Tables ........................................................................................................................ x
Chapter 1......................................................................................................................................... 1
1. Introduction ............................................................................................................................ 1
Chapter 2......................................................................................................................................... 3
2. Ladle Furnace .......................................................................................................................... 3
2.1. Primary Functions of Ladle Furnace ................................................................................. 4
2.1.1. Temperature control................................................................................................. 4
2.1.2. Stirring and Injecting ................................................................................................. 5
2.1.3. De-oxidation.............................................................................................................. 5
2.1.4. Desulphurization ....................................................................................................... 5
2.1.5. Removal of slag .......................................................... Error! Bookmark not defined.
Chapter 3......................................................................................................................................... 8
3. Fluorspar ................................................................................................................................. 8
3.1. Role of fluorspar in the slag ............................................................................................. 8
3.2. Phase relation of fluorspar with different oxides ............. Error! Bookmark not defined.
3.3. Evaluation of CaF2-CaO-SiO2 System ................................................................................ 9
3.4. Optical Basicity and Sulphide Capacity of CaF2 based slags............. Error! Bookmark not
defined.
3.5. Effect of CaF2 on viscosity of Slag...................................... Error! Bookmark not defined.
3.5.1. Explanation for the Decrease in Viscosity of CaF2-SiO2 Slag with CaF2 additions
Error! Bookmark not defined.
3.6. Effect of Fluorspar on Refractories ................................................................................ 10
3.7. Effect of CaF2 on the binder .............................................. Error! Bookmark not defined.
Chapter 4....................................................................................................................................... 13
4. Study of Phase Diagram to get lower Liquidus Temperature ............................................... 13
4.1. CaO-MgO-Al2O3-CaF2 System ......................................................................................... 13
4.2. CaO-SiO2-Al2O3-CaF2 System .......................................................................................... 14
4.3. CaO.SiO2-FeOx-CaF2 Ternary Phase Diagram ................................................................. 16
4.4. CaO-SiO2-Al2O3-MgO-CaF2 Slag system .......................................................................... 17
vi
 4.5. Al2O3-CaO-MgO-SiO2 Slag system .................................................................................. 19
Chapter 5....................................................................................................................................... 21
5. Experimental Work ............................................................................................................... 21
5.1. Objectives ....................................................................................................................... 21
5.2. Steel grades and respective slag system chosen ........................................................... 22
5.2.1. Grade of steel.......................................................................................................... 22
5.2.2. Slag system.............................................................................................................. 22
5.2.2.1. Slag Composition for Silicon-killed Steel ......................................................... 22
5.2.2.2. Slag Composition for Aluminium-killed Steel .................................................. 22
5.3. Experiment procedures .................................................................................................. 23
5.4. Laboratory Equipment ................................................................................................... 23
5.4.1. Coreless Induction Furnace..................................................................................... 24
5.4.1.1. Structure of Induction furnace ........................................................................ 25
5.4.2. Power system .......................................................................................................... 26
5.4.3. Crucible ................................................................................................................... 27
5.4.4. Mould ......................................................................... Error! Bookmark not defined.
5.4.5. Thermocouple ......................................................................................................... 27
5.5. Slag Samples used .......................................................................................................... 29
5.5.1. CaO- SiO2-CaF2 Slag system ..................................................................................... 29
5.5.2. CaO-Al2O3-CaF2 Slag system .................................................................................... 30
5.5.3. CaO-MgO-SiO2 Slag system ..................................................................................... 32
5.5.4. CaO-MgO-Al2O3 Slag system ................................................................................... 33
5.5.5. CaO-Al2O3-SiO2-MgO Slag system ........................................................................... 35
5.5.6. CaO-Al2O3-SiO2-MgO-CaF2 Slag system................................................................... 37
DTA Analysis of CaO-Al2O3-SiO2-MgO-CaF2 Slag system ................................................... 38
6. Summary and Conclusions .................................................................................................... 39
7. References ............................................................................................................................ 41

vii
viii
List of Figures
Figure 1: Construction of Ladle furnace[25] ..................................................................................... 3
Figure 2: Activity ratio of Oxygen: Sulphur in liquid iron at 1600 0C for oxide-sulphide
equilibrium[2] ................................................................................................................................... 6
Figure 3: Equilibrium sulphur partition ratio between liquid iron with dissolved Aluminium and
CaO-Al2O3 slags[2]............................................................................................................................. 6
Figure 4: CaO-CaF2 binary phase diagram [10] .................................. Error! Bookmark not defined.
Figure 5: Ternary Phase diagram [10] ............................................................................................... 9
Figure 6: Solubility of CaO vs SiO2 concentration in the slag[10] ................................................... 10
Figure 7: Effects of temperature and the contents of CaF2 or Al2O3 on the viscosity of the CaO-
SiO2-10 wt. % MgO for B=1 [29] ......................................................... Error! Bookmark not defined.
Figure 8: Effects of temperature and the contents of CaF2 or Al2O3 on the viscosity of the CaO-
SiO2-10 wt. % MgO for B=1.3 [29] ...................................................... Error! Bookmark not defined.
Figure 9: The activation energy for the viscous flow of the melts as a function of glass
compositions [29]............................................................................... Error! Bookmark not defined.
Figure 10: Penetration depth of fluoride ions in refractory with the % of CaF2 [13] ...................... 12

Figure 11: Backscattered Electron Image of refractory lining. Green dots shows Fluorine
particles [13] .................................................................................................................................... 12
Figure 12: Viscosity of slag vs CaF2 content [13]............................................................................. 11
Figure 13: Penetration depth in the refractory vs CaF2 content [13] ............................................. 11
Figure 14: Phase diagram of CaO-SiO2-CaF2 liquidus isotherm [13] .. Error! Bookmark not defined.
Figure 15: Grains of coming out of refractory [13] ............................ Error! Bookmark not defined.
Figure 16: CaO-MgO-Al2O3-CaF2 system with 10% Al2O3 [3] .......................................................... 13
Figure 17: CaO-MgO-Al2O3-CaF2 system with 20% Al2O3 [3] .......................................................... 13
Figure 18: CaO-MgO-Al2O3-CaF2 system with 40% Al2O3 [3] .......................................................... 13
Figure 19: CaO-SiO2-Al2O3-CaF2 Ternary phase diagram with Al2O3 = 10% showing isoliquidus
lines [3] ........................................................................................................................................... 14
Figure 20: CaO-SiO2-Al2O3-CaF2 system with 2% CaF2 showing isoliquidus lines [3] ..................... 14
Figure 21: CaO-SiO2-Al2O3-CaF2 system with 4% CaF2 showing isoliquidus lines [3] ..................... 14
Figure 22: CaO-SiO2-Al2O3-CaF2 system with 8% CaF2 showing isoliquidus lines [3] ..................... 15
Figure 23: CaO-SiO2-Al2O3-CaF2 system with 6% CaF2 showing isoliquidus lines [3] ..................... 15
Figure 24: CaO-SiO2-Al2O3-CaF2 system with 10% CaF2 showing isoliquidus lines [3] ................... 15

ix
Figure 25: CaO-SiO2-FeOX-CaF2 system showing immiscible liquid phases at 1400 0C with CaO:
SiO2 = 1[3] ....................................................................................................................................... 16
Figure 26: CaO- SiO2-FeOX-CaF2 system showing immiscible liquid phases at 1400 0C with CaO:
SiO2 = 2[3] ....................................................................................................................................... 16
Figure 27: CaO-SiO2-MgO-Al2O3-CaF2 system isoliquidus lines with 10% Al2O3 and 4% CaF2 [3] .. 17

Figure 28: CaO-SiO2-MgO-Al2O3-CaF2 system isoliquidus lines with 10% Al2O3 and 2% CaF2 [3] .. 17
Figure 29: CaO-SiO2-MgO-Al2O3-CaF2 system isoliquidus lines with 10% Al2O3 and 6% CaF2 [3] .. 17
Figure 30: CaO-SiO2-MgO-Al2O3-CaF2 system isoliquidus lines with 10% Al2O3 and 8% CaF2 [3] .. 17
Figure 31: CaO-SiO2-MgO-Al2O3-CaF2 system isoliquidus lines with 10% Al2O3 and 10% CaF2 [3] 18
Figure 32: CaO-Al2O3-SiO2-MgO slag system for 5% Al2O3 [3] ........................................................ 19
Figure 33: CaO-Al2O3-SiO2-MgO slag system for 15% Al2O3 [3] ...................................................... 19
Figure 34: CaO-Al2O3-SiO2-MgO slag system for 25% Al2O3 [3] ...................................................... 20
Figure 35: Induction furnace in operation .................................................................................... 24
Figure 36: Induction furnace mounted ......................................................................................... 24
Figure 37: Internal design of induction furnace ........................................................................... 25
Figure 38: Inductotherm ............................................................................................................... 26
Figure 39: Graphite crucible ......................................................................................................... 27
Figure 40: Mould made up of mild steel.......................................... Error! Bookmark not defined.
Figure 41: Thermocouple and voltmeter ...................................................................................... 27

x
List of Tables
Table 1: Percentage of Liquid CaO vs percentage of total CaO in CaO-CaF2 system [10].......... Error!
Bookmark not defined.
Table 2: %CaO at saturation with different binary components at 1600 0C [10] .... Error! Bookmark
not defined.
Table 3: Optical basicity of the slag components [10] ....................... Error! Bookmark not defined.
Table 4: Optical basicity and the Sulphide capacity of the slag [10] . Error! Bookmark not defined.
Table 5: Activation energy for viscous flow of CaO-SiO2-MgO-CaF2 & CaO-SiO2-MgO-Al2O3 slag
[29] ..................................................................................................... Error! Bookmark not defined.

Table 6: Viscosity and Surface Tension of Slag depending on the Slag Constituent [13] ............... 11
Table 7: Composition of Binder in MgO based refractories [4] ........ Error! Bookmark not defined.
Table 8: Liquidus temperature for various binary composition of CaO- SiO2-CaF2 slag system .. 29
Table 9: Liquidus temperature for various binary composition of CaO-Al2O3-CaF2 slag system . 30
Table 10: Liquidus temperature for binary composition of CaO-SiO2-MgO slag system ............. 32
Table 11: Liquidus temperature for binary composition of CaO-Al2O3-MgO slag system ........... 33
Table 12: Liquidus temperature for binary composition of CaO-Al2O3-SiO2-MgO slag system ... 35
Table 13: Liquidus temperature for CaO-Al2O3-SiO2-MgO-CaF2 slag system ............................... 37

xi
 Chapter 1

1. Introduction
Primary steelmaking is used for rapid refining of hot metal, DRI and steel scrap into finished steel.
This refining is done at macro level to achieve certain grades of steel with broader specifications.
The micro level adjustment in order to get a precise steel quality, uniformity in composition and
temperature for a given grade of steel is not achieved in primary steelmaking. To get the final
specific compositions, the steel is refined again and the process so called is secondary
steelmaking.
Ladle is a bucket shaped container, which has a capacity between 30 to 200 tons of steel. Many
processes can be performed in the ladle furnace like vacuum degassing, inert gas purging. The
main objective of the ladle refining is de-oxidation, desulphurization of liquid steel. During ladle
refining, we use fluorspar as a fluxing agent in special conditions where we need slag having low
liquidus temperature. Vacuum degasser is an equipment used to create a vacuum suction over
the ladle, which helps in removal of dissolved Hydrogen, Carbon, and Oxygen present in the melt
to make the steel pure. Purging inert gas helps in stirring the melt with added reactive metal like
Aluminium, which removes the oxygen dissolved in the melt.
Secondary steelmaking is the intermediate process between primary steelmaking and the casting
process. Its main objective is to finalize the composition of the steel produced after the primary
refining process. Major impurities that have to be removed in this refining are Oxygen, Nitrogen,
Hydrogen, Sulphur and Phosphorous. These impurities degrades the strength, ductility and
corrosion strength.
Chemical adjustment of various elements like Sulphur, Phosphorous, and Carbon are done. The
molten steel here is alloyed with some of the alloying elements like Chromium, Magnesium,
Manganese, Nickel etc., to give the desired strength. During the secondary refining process, the
temperature of the molten metal is homogenized. Desulphurization is one of the objective of the
secondary refining process, as the final percentage of Sulphur is reduced to desired value.
Without any heating arrangements, the temperature drops to 60-100 degree Celsius between
the taping from primary steel making and continuous casting of molten steel. So ladle furnace in
1
special units is used for heating and maintaining uniform temperature while the secondary
refining takes place.
The operating temperature of ladle furnace depends on the liquidus temperature of molten steel.
For steel, as the percentage of Carbon increases in the binary mixture of Iron and Carbon, there
is a lowering of liquidus temperature. To operate at lower temperature the slag also needs to
have a low liquidus temperature. Fluorspar when added reduces the liquidus temperature as the
fluoride ions in it breaks the network of the major slag constituents. Fluorspar are used majorly
for high carbon steel but it has environmental problems so some alternative must be looked upon
where fluorspar is not used yet lower liquidus can be attained.
For the major components of the slag, we can get liquidus temperature of the slag at different
composition from the binary, ternary, quaternary phase diagram depending on the number of
components the slag has. After the examination, experiments can be done to get the minimum
liquidus temperature. The composition having the lowest liquidus temperature can be tested and
used for the ladle refining of low melting high carbon steel.

2
 Chapter 2

2. Ladle Furnace
Ladle furnace is generally used to relieve ladle used in secondary refining process. Few
metallurgical reactions are easily and best performed in the ladle furnaces. The simplest
treatment of steel in the ladle is done when tapping stream is used for the addition of deoxidizers,
fluxes and slight quantity of alloying elements. Apart from these ladle furnace has secondary
functions like addition of alloying element to get the desired quality of steel, addition of suitable
fluxes for deep desulphurization of the steel, addition of cored wire, which helps in controlling
the morphology. Besides this, it also acts as a buffer for the downstream manufacturing in the
steelmaking process.

Figure 1: Ladle furnace[24]

Several secondary steelmaking units are installed in the steelmaking shop where ladle furnace are
taken to and the refining process takes place.

3
2.1. Primary Functions of Ladle Furnace

 Temperature control
 Homogenization of the melt
 Deoxidation
 Desulphurization

2.1.1. Temperature control

The de-oxidation reaction occurring in the ladle is exothermic due to which heat is generated.
However, there is a loss of heat through radiation from the top surface of the melt as the
temperature of the melt is very high. Heat is also lost by heating of the ladle lining and the flow
of heat flux from ladle lining to the shell by the conduction. The temperature drop by just keeping
the steel on hold is about 0.2 to 0.3 0C per minute. This can be even larger for the smaller ladle,
which has a high surface to volume ratio. This rate of temperature drop keeps on decreasing and
eventually leads to a steady state where there is a steady flow of heat between the slag layer and
the lining.
Tapping of the refines steel must be done at a specific temperature so it meets the critical
temperature requirements for the casting process thereafter. The heat loss can be predicted by
considering the temperature of the melt before and after tapping, thickness of the slag layer,
thickness of the ladle lining, the stirring effects, holding time and from the thermodynamics of
the alloying elements. The overall control over the steel temperature is done with the help of an
electric arc furnace that has three electrodes that is used for generating heat through arc heating.
In most of the Ladle furnaces, the temperature can be raised by about 4-6 0C /min.
The graphite rods installed in it conducts electricity out of which heat is generated which is used
in the reheating of the liquid steel. The temperature and the chemical composition of the steel is
homogenized by stirring with the help of inert gas like Argon. Electromagnetic stirring can also
done be used for better heat transfer.

4
2.1.2. Stirring and Injecting

The temperature of the steel coming out of the furnace must have minimum fluctuations for
most of the continuous casting methods. For this, there are ladle-stirring stations that stirs the
entire melt to maintain a uniform temperature. The stirring is done through the injection of Argon
gas through the lance. It can also be stirred with the help of electromagnetic coil.
Stirring is done in the ladle furnace with the help of Porous plug. It helps in homogenization of
the molten melt by gas stirring. This arrangement is done at the bottom of the ladle and is used
for normal stirring of the melt by passing the jet of Argon gas through this arrangement.
Supply of gas into the ladle is automatically done as the ladle is kept on the transfer car. In
addition to this wire feeder is also kept at the stirring station. The wire feeder runs the wire into
the molten steel at a desired speed through the refractory covered lance.

2.1.3. De-oxidation

Steelmaking involves selective oxidation of impurities in liquid iron. This involves oxidation of
Carbon, Silicon and other solute elements. During the solidification of steel, some of the Oxygen
gets dissolved in the liquid steel. During solidification of the steel, the oxygen comes out, as the
solubility of oxygen is very small in solid steel. Escape of excess oxygen results in defects like
blowholes. Some undesirable non-metallic inclusions are also formed which hamper the physical
properties of the cast metal. So the removal oxygen from the melt becomes necessary. [2]

The oxygen is removed by the process of de-oxidation after primary steelmaking and before the
metal is teemed into continuous casting mould or ingot. The process is done into ladle furnace.
For this, de-oxidizers are added which reacts with dissolved oxygen to form a mixture of oxides
in the form of precipitates. When Aluminium is used, it is called Aluminium-killed steel and when
Silicon is used, it is called Silicon-killed steel. [2]

2.1.4. Desulphurization

Sulphur primarily comes from the coal used in the ironmaking process. It also comes from
impurities in iron and also from the fluxes used making slag. It reacts with metal oxide to form
metal sulphide by the following equation:
5
[S] + (O2-) = (S2-) + [O]

Figure 2: Activity ratio of Oxygen: Sulphur Figure 3: Equilibrium sulphur partition

in liquid iron at 1600 0C for oxide-sulphide ratio between liquid iron with dissolved
equilibrium[2] Aluminium and CaO-Al2O3 slags[2]

Reaction coefficient, K= (aS2-)[hO]/(aO2-)[hS]

We can interpret from the above figure that Barium is the strongest deoxidizer followed by
Calcium and Magnesium is even weaker. Since Barium is economically costlier, so we can use
Calcium as the desulphurizing agent. [3]
The Sulphide capacity be written as:
Cs= (Ws)(p02)/(pS2)
Similarly, the sulphur partition ratio is the ratio of weight percent of Sulphur in slag and metal.
Ls = (Ws)/[Ws] = C’S/[hO]
We can interpret that lower oxygen percentage in the metal favours the desulphurization
process. Dissolved Oxygen percentage in the slag is determined by the weight percentage of
deoxidizers. This is supported by (Figure 2).

6
The desulphurization with the CaO is written as:
CaO(s) + S =CaS(s)+ O
logK = -5304/T + 1.191
Activity of CaO in Al2O3-based slags is much larger than the activity of CaO in SiO2-based slags. So
for the desulphurization process, SiO2 in the slag is undesirable. It can be seen in the following
equation. [3]
log (Cs) = 3.44( XCaO + 0.1 XMgO - XSiO2 - 0.8 XAl2O3) - 9894/T + 2.05
Since Aluminium is superior to Silicon, it has to be added as deoxidizer.
log (Ls) = log C’s – log hO
So, Log (Ls) = log Cs – 936/T + 1.375 – log hO
log hO = 1/3[-64000 + 20.57 – 2 log WAl + log aAl2O3 ]
log (Ls) = log Cs + 2/3 log WAl – 1/3 log aAl2O3

For desulphurization process, powder injection can also be used. The powder injected can be Ca-
Si alloy having 30% Ca and 60% Si [32]. Metallic Calcium when combined with Sulphur produces a
very stable compound called Calcium Sulphide. Since pure Calcium is very reactive in nature as it
reacts instantaneously with water, it is mixed with Silicon. Adding 4 kg of Calcium Silicon alloy to
1 ton of steel with decrease the Sulphur content by a fraction of four. [2] In general, by adding this
much amount of Calcium Silicon alloy, the Sulphur content is reduced from 0.016% to 0.004% [2]
In the steel where Silicon is not preferred, Magnesium-lime combination is used as alloying
element instead of Silicon. Magnesium-lime combination is also an excellent desulphurizer,
which can also combine with the dissolved oxygen present in the melt. This helps lime in the
desulphurization process.
CaO + FeS → CaS + FeO

Hence, lime plays a primary role also in the desulphurization process.

7
 Chapter 3

3. Fluorspar
Fluorspar also known as Calcium Fluoride. It has a chemical formula of CaF 2 .
Metallurgical grade: 75-80% pure Density: 3.180 g/cc
Melting Point: 761 0C Boiling point: 2500 0C
Occurrence: Generally found as vein deposit mostly along with the mineral deposit.
Health hazards: It has a potential health hazards especially on the lungs when inhaled.

Fluorspar is called as the black sheep in the steel industry because it does the maximum damage
to the refractories than any other components. Because of it in most of the plants, CaF2 is banned.
Fluorspar has few advantages in the steel making process but it has many disadvantages too.
3.1. Role of fluorspar in the slag
a) For increasing the solubility of the basic compounds in the slag.
b) For maintaining the slag fluidity even if, the temperature goes down.

8
3.2. Evaluation of CaF2-CaO-SiO2 System

Figure 4: Ternary Phase diagram Error! Reference source not found.

Addition of SiO2 to the CaO-CaF2 system increases the maximum solubility limit of CaO. However,
beyond 16% of SiO2 the solubility again goes down. The maximum solubility at 1600 0C is achieved
at the intersection lines in the diagram. The composition of slag at this point is %CaO = 72, %SiO2
= 16, %CaF2 = 12. The saturation solubility of CaO in the CaF2-CaO-SiO2 system at 1600 0C is
plotted in next figure.

9
Figure 5: Solubility of CaO vs SiO2 concentration in the slag Error! Reference source not This plot
found.
(Figure 6)
clearly shows that if the percentage of SiO2 is increased the maximum percentage of CaO in the
melt so that the composition has liquidus below 1600 0C also increases but only to a certain
extent, at that point CaO has the maximum solubility. This also suggests that only SiO 2 does not
solely increase the solubility and hence fluorspar addition is required.

3.3. Effect of Fluorspar on viscosity of slag and on refractories

The refractory made for the refining purpose is has a lining of MgO because it is basic itself and
cannot be attacked by the basic slag. Addition of fluorspar decrease the viscosity of the alumina-
silicate slag. If the concentration of CaF2 is increased, then the penetration of the alumina-silicate
slag in the grain boundary of the MgO lining of the refractory is observed. It is because the slag
becomes less viscous and hence the penetration becomes easier. The erosion happening at the
MgO lining speed up the corrosion process. The corrosion rate gets reduced if the percentage of
magnesium is made to its saturation value in the melt.

10
Table 1: Viscosity of Slag depending on the Slag Constituent [12]

Chemical constituents and composition

Viscosity
S. No CaO Al2O3 SiO2 MgO CaF2
wt% wt% wt% wt% wt% poise
1 56.5 30.5 8 5 0 2.1
2 51.6 27.9 8 5 7.5 0.8
3 47 25 8 5 15 0.6

From the above table it can be inferred that he depth of penetration of slag into the refractories
is proportional to the CaF2 content. The penetration of slag happens through the pores present
in the refractories and is dependent on other factors like the viscosity and the interfacial tension
between the slag and the refractory walls. With the increase of the fluorspar content from 0 to
15 weight percent, viscosity of the slag decreased from 2.1 to 0.6 poise.

The following figures clearly shows the relationship between the CaF2 content in the slag and the
penetration depth of slag into refractories and between the CaF2 concentration in the slag and
the viscosity of the slag.

Figure 6: Viscosity of slag vs CaF2 content [12]Figure 7: Penetration depth in the refractory
vs CaF2 content [12]

11
The damage occurred to the refractory is mostly because of the reaction between the refractory
constituents and the slag. The damage occurred could be physically viewed through the Back
Scattered Electron imaging technique.

Figure 8: Penetration depth of fluoride Figure 9: Backscattered Electron Image of

ions in refractory with the % of CaF2 [12] refractory lining. Green dots shows Fluorine
particles [12]

If the percentage of CaF2 added to the slag is increased a lot then the MgO from the refractory
gets dissolved into the slag.

12
 Chapter 4

4. Study of Phase Diagram to get lower Liquidus Temperature

4.1. CaO-MgO-Al2O3-CaF2 System

Figure 10: CaO-MgO-Al2O3-CaF2 system with Figure 11: CaO-MgO-Al2O3-CaF2 system

10% Al2O3 [4] with 20% Al2O3 [4]

Figure: 16-18
For CaO-MgO-Al2O3-CaF2 quaternary
system, the lines represents isothermal
liquidus surface in an inert atmosphere
with 10, 20 and 40 mass % respectively
of Al2O3.
Figure 12: CaO-MgO-Al2O3-CaF2 system with 40%
Al2O3 [4]

13
4.2. CaO-SiO2-Al2O3-CaF2 System

Figure 13: CaO-SiO2-Al2O3-CaF2 Ternary phase diagram with Al2O3 = 10% showing isoliquidus
lines [4]

CaO-SiO2-Al2O3-CaF2 quaternary slag system has a very low liquidus region for higher fluorspar
region. Since fluorspar is very effective in lower liquidus temperature, hence it is necessary to
consider the composition of CaO, SiO2, Al2O3, and CaF2 with varying CaF2 additions.
Following are ternary diagram of CaO-SiO2-Al2O3 with varying CaF2 additions:

Figure 14: CaO-SiO2-Al2O3-CaF2 system with Figure 15: CaO-SiO2-Al2O3-CaF2 system with
2% CaF2 showing isoliquidus lines [4] 4% CaF2 showing isoliquidus lines [4]

14
Figure 17: CaO-SiO2-Al2O3-CaF2 system with
Figure 16: CaO-SiO2-Al2O3-CaF2 system with
6% CaF2 showing isoliquidus lines [4]
8% CaF2 showing isoliquidus lines [4]

Figures: 22-24
For CaO-SiO2-Al2O3-CaF2 quaternary
system, the lines represents
crystallisation temperatures with 2, 4,
6, 8 and 10 mass % of CaF2 respectively.
These are deduced from viscosity vs.
Figure 18: CaO-SiO2-Al2O3-CaF2 system temperature curves.
with 10% CaF2 showing isoliquidus lines [4]

From the above diagrams, the following points can be concluded:

 As the fluorspar additions are increased the liquidus temperature can be assume to be
lowered.
 The low temperature liquidus is much nearer to SiO2 vertex. So it can be concluded that SiO2
is much effective in lowering the liquidus temperature than the addition of Al2O3.
 Temperature of around 1400 degree Celsius can be achieved for 50 wt% of CaO provided the
fluorspar content is higher.
 As from the previous figure it was concluded that only binary mixture of CaO and Fluorspar
can’t have the lower liquidus temperature so the addition of SiO2 becomes very significant.

15
4.3. CaO.SiO2-FeOx-CaF2 Ternary Phase Diagram

Figure 19: CaO-SiO2-FeOX-CaF2 system Figure 20: CaO- SiO2-FeOX-CaF2 system

showing immiscible liquid phases at 1400 showing immiscible liquid phases at 1400
0C with CaO: SiO = 1[4] 0C with CaO: SiO = 2[4]
2 2

Following conclusions can be made out of the figure:

 The increasing percentage of the SiO2 lowers the liquidus temperature as the miscible phase
of liquid is larger for CaO: SiO2 ratio = 1 as compared to CaO: SiO2 ratio = 2.
 CaF2 is more effective in attaining lower liquidus as the liquid phase is closure to CaF2 vertex.
 Temperature of 1400 degree Celsius can be attained by CaO.SiO2 with little addition of CaF2.
FeOx does not have much importance, as its percentage is very less in the ladle slag.

16
4.4. CaO-SiO2-Al2O3-MgO-CaF2 Slag system

Figure 22: CaO-SiO2-MgO-Al2O3-CaF2 Figure 21: CaO-SiO2-MgO-Al2O3-CaF2

system iso liquidus lines with 10% Al2O3 and system iso liquidus lines with 10% Al2O3
2% CaF2 [4] and 4% CaF2 [4]

Figure 23: CaO-SiO2-MgO-Al2O3-CaF2 Figure 24: CaO-SiO2-MgO-Al2O3-CaF2

system isoliquidus lines with 10% Al2O3 and system iso liquidus lines with 10% Al2O3 and
6% CaF2 [4] 8% CaF2 [4]

17
 Figure: 27-31
For CaO-SiO2-MgO-Al2O3-CaF2 quaternary
system, the lines represents crystallisation
temperatures with 2, 4, 6, 8 and 10 mass
Figure 25: CaO-SiO2-MgO-Al2O3-CaF2 % of CaF2 respectively. These are deduced
system isoliquidus lines with 10% Al2O3 and from viscosity vs. temperature curves
10% CaF2 [4]

The following conclusion can be made out of the above diagrams:

 The liquidus temperature of the slag goes down as the percentage of fluorspar is increased.
 The lower liquidus composition is closest to SiO2 but for higher composition of CaO, the
isoeutectine line of lower liquidus is somewhat in the middle.
 MgO has very less effect in lowering the liquidus temperature, so in order to get the lower
liquidus temperature the percentage of MgO has to be minimum.

18
4.5. Al2O3-CaO-MgO-SiO2 Slag system

Figure 26: CaO-Al2O3-SiO2-MgO slag system for 5% Al2O3 [4]

Figure 27: CaO-Al2O3-SiO2-MgO slag system for 15% Al2O3 [4]

19
Figure 28: CaO-Al2O3-SiO2-MgO slag system for 25% Al2O3 [4]

Following conclusions can be made out of the above diagrams:

 As the percentage of Aluminium increases, the liquidus temperature decreases up to 15%
of Aluminium and then increases.
 Increase in percentage of MgO does not result into lowering of the liquidus temperature.
 Temperature of 1400-degree Celsius can be achieved to the adequate basicity and SiO2
percentage for 15% Alumina content without any addition of fluorspar.

20
 Chapter 5

5. Experimental Work
5.1. Objectives

Most of the work during this project is regarding the minimization of the liquidus temperature of
slag used in the secondary refining process.

The liquidus temperature of High Carbon steel is 1425 0C to 1440 0C, which is relatively lower
than the liquidus temperature of low Carbon steel, which has a liquidus temperature of 1500 0C

The slag hence formed in the steelmaking process of high carbon steel needs to have a lower
liquidus temperature.

Fluorspar is used so far for the secondary steelmaking process as a fluxing agent as it reduces the
liquidus temperature by a large extent. Unfortunately, it has severe effect on ladle refractory and
has environmental problems too. Hence, its use has to be minimized.

Without the use of fluorspar as fluxing agent, various slag system needs to be studied which has
lower liquidus temperature. The chosen slag system must be able to carry out the necessary
functions and resemble the commonly used slags in terms of physio-chemical properties. Also, it
must not have any adverse effect on the properties of steel being refined.

The aimed slag system depends on the grade of steel we want to produce. For Silicon-killed steel,
slag has a higher percentage of SiO2 and for Aluminium-killed steel, slag has a higher percentage
of Al2O3.

The chemical composition of the slag chosen should have high CaO, as it is necessary to maintain
high basicity of the slag in order to maintain its refining capability (e.g. removal of sulphur).

The slag has to be saturated with MgO so that the basic lining of the refractory is not damaged.
MgO solubility depends on the basicity of the slag so CaO percentage also matters in the slag to
have lower liquidus temperature of the slag.

The chosen components should not environmental effects.

21
5.2. Steel grades and respective slag system chosen

5.2.1. Grade of steel

The grade of steel concerned is High Carbon steel. The percentage of Carbon in this steel is
between 0.6 – 1.2. The liquidus temperature of the binary compound therefore obtained is in
between 1450 to 1490 degree Celsius. For Carbon content of 1.5% the liquidus temperature is
lowered to 1425 degree Celsius. Hence, as the percentage of Carbon increases, the liquidus
temperature of the alloy is decreased. The maximum operating temperature is reduced to save
the energy. The slag formed should also have low liquidus temperature because otherwise the
slag will be much crusty and will not have enough fluidity to carry on the diffusion process that is
important in the refining of steel.

5.2.2. Slag system

5.2.2.1. Slag Composition for Silicon-killed Steel

The primary component is CaO as it is required for high basicity of slag and to get low liquidus
temperature. MgO is needed to maintain its saturation in the slag to minimize the refractory
wear. SiO2 in the slag is higher as Silicon is used to deoxidize the melt. Al2O3 is added to get the
lower liquidus temperature. The simplified composition is:
% CaO = 48 % MgO = 12
% SiO2 = 30 %Al2O3 = 10
5.2.2.2. Slag Composition for Aluminium-killed Steel

The primary component is CaO as it is required for high basicity of slag and to get low liquidus
temperature. MgO is needed to maintain its saturation in the slag to minimize the refractory
wear. SiO2 in the slag is higher as Aluminium is used to deoxidize in the melt. SiO2 is added to
get the lower liquidus temperature. The simplified composition is:
% CaO = 57 % MgO = 8
%Al2O3 = 30 % SiO2 = 5

22
5.3. Experiment procedures

1 Oxides powders that constitute major components of the slag are taken. It has 95% purity
and is in the fine powdered form.
2 The composition of slag with lower liquidus is marked out. Different powders constituting
the slag are taken separately and measured in the weight balance machine in the Ferrous
Process Laboratory. The final weight of the entire sample is made 50 g.
3 The powders are mixed together thoroughly to make a sample. Like this, various samples
are made with varying compositions.
4 The powders are poured into graphite crucible. The crucible is then placed into the
induction furnace. The furnace is operated at 30 kW.
5 The entire mixture is melted and then allowed to cool until it is solidified. This was done
to ensure that the composition is macroscopically uniform.
6 The mixture is heated again slowly by slowly increasing the power to the furnace and the
phase change of sample is observed.
7 One the droplets seems to come out which suggests that the sample has reached the
solidus temperature. The power is decreased by 2 kWhr and the melt is allowed to liquefy.
The power is decreased because the crucible is at a higher temperature than the melt as
it is heated first because the heating due to induction happens solely in the crucible. This
is because graphite crucible is conducting but the slag is non conducting. The heat is
transferred to the melt through conduction which is not instantaneous. If the power is
not reduced than the temperature of the melt will increase because the steady state has
not reached. To reduce overheating, the power is reduced.
8 As the sample is half melted, thermocouple is dipped inside. The thermocouple is kept
for few seconds until the reading in the voltmeter gets stable. The reading is noted.
9 The power is shut down to zero, the melt is power into the mould with the help of pair of
tongs, and the crucible is kept back into the furnace to start the new experiment.
10 The slag formed is kept in a sachet for further analysis.

23
5.4. Laboratory Equipment
The experiments were performed in Ferrous Process Laboratory, IIT Bombay

5.4.1. Coreless Induction Furnace

Figure 29: Induction furnace in operation Figure 30: Induction furnace mounted

The furnace has a capacity of 1 kg capacity. It can work at the maximum frequency of 9.65 kHz.
The heat produced is because of electromagnetic induction because of the alternating current
produced in the coil. The maximum attainable temperature is 1700 0C. The varying magnetic field
induces electric field in any conductor placed in the field. Metals can be melted inside by directly
placing it into the non-conducting crucible into the furnace. In order to melt non-conducting
substances slag we need to place into highly conducting crucible and that it should not melt itself.
Hence, for the purpose graphite crucible is best suited. Since for a solenoid ideally there is no
magnetic field outside. Therefore, it is safe to operate as heating cannot happen even after. The
high-density graphite crucible can hold 100 grams of slag mixture in it.

24
5.4.1.1. Structure of Induction furnace

Figure 31: Internal design of induction furnace

Following are the major components of induction furnace:

 Outer Shell: Outer shell is made up of Mild steel. The outer cover is made up of sheet of mild
steel. The total outer volume is 40cm*40cm*40cm.
 Inner Lining of furnace: Inner lining is made up of non-conducting highly refractory material.
For this purpose Magnesia is preferred as they have melting point as high as 2800 0C.
 Heating element: In the furnace there is copper coil turned into the form of solenoid. The
copper coil is made up of hollow copper pipe. The Alternating current is passed through it,
which induces current inside the conductor placed inside it.
 Cooling agent: Water is flown through the hollow copper coil, which helps in cooling down
the refractory and the cooling agent to minimize the wear. The water is flown through the
pipe at the rate of 60 litres per minute.
 Power Supply: The final power is a uniform sinusoidal electromagnetic current that is
supplied by the transformer. The frequency of the can be fed up to 9.65 kHz to produce the
maximum heat.

25
5.4.2. Power system

Figure 32: Power Supply System

This is a power supply system with Transformer, Thyristor, Inductor, Fuse, Choke installed in it.
Following are the main components. The current goes in the following order.
 Main Circuit Breaker: MCB is installed at the top corner from where the current comes in. It
is very essential to cut the power completely in case of any mishap during operation.
 Phase Converter: Three-phase power of 440 V is fed into the circuit. Three phase is
converted into Two phase.
 Thyristor: AC is now converted into pulse DC with the help of Thyristor and the current
produced has a uniform polarity but does not have a uniform strength.
 Choke: The non-uniform DC current is converted into uniform current by superimposing
various variable DC current with different phases. The outgoing current is uniform to get a
pure sinusoidal waveform in latter stages of the circuit.
 Inverter: The invertor is used to convert the uniform DC current into sinusoidal AC
waveform. The frequency of the output can be changed manually with the help of a meter.
Finally, the AC current is fed to the furnace through the insulating wire.
26
5.4.3. Crucible

Composition: High Density Graphite

Outer Diameter = 5.2cm
Inner Diameter = 3.3cm
Outer length = 12.5 cm
Inner depth = 11 cm
Inner volume = 94 ml

Made by Hot Isostatic Pressure technique by using highly pure

graphite powder. The crucible was placed in the furnace. It
generally lasts for 10 heats as the oxides in the slag oxidizes
the Carbon present in it into CO2 resulting into diminish of the
crucible thickness. So only selective and careful experiments
Figure 33: Graphite crucible
needs to be done.
.
5.4.4. Thermocouple

Figure 34: Thermocouple and voltmeter

The lab has B-Type thermocouple The two electrodes has the alloy composition of
70%Pt/30%Rh|94%Pt/6%Rh thermocouple which can measure temperature upto 1800 degree

27
Celsius. The higher temperature measurement is limited by the Silica bulb used to protect the
thermocouple as it melts while the thermocouple is dipped into the melt.
The potential difference between the wires in thermocoupe is sent into the Voltmeter through
wire. The voltage received is in millivolts and is displayed at the LED display at the from of the
multimeter. The display needs to be noted manually. The cold junction correction is done done
so the results have some errors. The temperature obtained is slightly lower than the actual value.

28
5.5. Slag Samples used
5.5.1. CaO- SiO2-CaF2 Slag system

Size of sample = 50g

Table 2: Liquidus temperature for various ternary composition of CaO- SiO2-CaF2 slag system

Components Composition Thermocouple Liquidus Temperature

S. No
(in slag) (wt. % ) reading (mV) (0C)
CaO 45
1. SiO2 55 17.7 1520
CaF2 0
CaO 70
2. SiO2 0 19.0 1610
CaF2 30
CaO 55
3. SiO2 30 14.9 1320
CaF2 15

CaO-SiO2-CaF2
1800
1610
1520
1600
Liquidus Temperature (0C)

1320
1400
1200
1000
800
600
400
200
0
CaF2 = 0% CaF2 = 30% CaF2 = 15%
SiO2 = 55% SiO2 = 0% SiO2 = 30%
CaO = 45% CaO = 70% CaO = 55%
Slag Composition

29
Following interpretations can be made out of the table:
 Without CaF2, the liquidus temperature is very high.
 Without having higher percentage of SiO2 in the slag also results in higher liquidus
temperature even if larger quantity of CaF2 is added.
 The minimum liquidus temperature is acquired only when both SiO2 and CaF2 is present
together in sufficient quantity.
 CaF2 along with SiO2 becomes a good fluxing agent rather than solely adding CaF2.
 SiO2 itself cannot attain lower liquidus temperature, so addition of CaF 2 for attaining lower
liquidus temperature is necessary.

5.5.2. CaO-Al2O3-CaF2 Slag system

Size of sample = 50g

Table 3: Liquidus temperature for various ternary composition of CaO-Al2O3-CaF2 slag system

Components Composition Thermocouple Liquidus Temperature

S. No
(in slag) (wt. % ) reading (mV) (0C)
CaO 50
1. Al2O3 50 18.1 1550
CaF2 0
CaO 57.5
2. Al2O3 37.5 17.3 1490
CaF2 5
CaO 55
3. Al2O3 35 16.7 1450
CaF2 10

30
 CaO-Al2O3-CaF2
1600
1550
1550
Liquidus Temperature (0C)

1490
1500
1450
1450

1400

1350

1300
CaF2 = 0% CaF2 = 5% CaF2 = 10%
Al2O3 = 50% Al2O3 = 37.5% Al2O3 = 35%
CaO = 50% CaO = 57.5% CaO = 55%
Slag Composition

Compare of liquidus temperature

1800
1600
1400
Temperature 0C

1200
1000
800
600
400
200
0
1 2 3
Composition

CaO-SiO2-CaF2 CaO-Al2O3-CaF2

The following interpretations can be made out of the above table:

 As the percentage of fluorspar is increased, there is reduction in the liquidus temperature.
 The lowering of the liquidus temperature is not as significant as in the case of SiO2
 This suggests that Al2O3 along with fluorspar do not serve as a good fluxing agent as SiO2
 Hence, the percentage of Al2O3 has to be minimum in the CaO containing slag.
31
5.5.3. CaO-MgO-SiO2 Slag system

Table 4: Liquidus temperature for ternary composition of CaO-SiO2-MgO slag system

S. Components Composition Thermocouple Liquidus Temperature

No (in slag) (wt. % ) reading (mV) (0C)
1. CaO 45 16.6 1440
SiO2 45
MgO 10
2. CaO 50 18.7 1590
SiO2 40
MgO 10
3. CaO 40 15.8 1380
SiO2 50
MgO 10

CaO-SiO2-MgO
1650
1590
Liquidus Temperature (0C)

1600

1550

1500
1440
1450
1380
1400

1350

1300

1250
MgO = 10% MgO = 10% MgO = 10%
SiO2 = 45% SiO2 = 40% SiO2 = 50%
CaO = 45% CaO = 50% CaO = 40%
Slag Composition

32
The following interpretations can be made out of the above figure:
 Addition of SiO2 to CaO results in reasonable decline in the liquidus temperature.
 MgO content is kept constant just to saturate the slag with MgO to preserve refractory
lining of the ladle furnace.
 Here in order to get lower liquidus, higher amount of SiO2 is required which is undesirable
for the ladle refining process as the basicity of the slag needs to be higher than 1.5.
 Therefore, so other fluxing agent should be mixed to get achieve a better basicity with a
low liquidus lag.

5.5.4. CaO-MgO-Al2O3 Slag system

Table 5: Liquidus temperature for ternary composition of CaO-Al2O3-MgO slag system

Components Composition Thermocouple Liquidus

S. No
(in slag) (wt. % ) reading (mV) Temperature (0C)
CaO 53
1. Al2O3 37 19.1 1610
MgO 10
CaO 40
2. Al2O3 52 17.6 1520
MgO 8
CaO 55
3. Al2O3 35 --- (very high)
MgO 20

33
 CaO-Al2O3-MgO
1800
1750 1700
Liquidus Temperature (0C)

1700
1650 1610
1600
1550 1520

1500
1450
1400
1350
1300
MgO = 15% MgO = 10% MgO = 8%
Al2O3 = 30% Al2O3 = 37% Al2O3 = 52%
CaO = 55% CaO = 53% CaO = 40%
Slag Composition

Comparision of liquidus temperature

1800
1600
1400
Temperature 0C

1200
1000
800
600
400
200
0
1 2 3
Slag Composition

CaO-SiO2-MgO CaO-Al2O3-MgO

Following interpretations can be made out of the above table:

 The ternary CaO-Al2O3-MgO slag system has a very high liquidus temperature isotherm.
 Even for heavy fluxing of Al2O3 to the major component CaO cannot result in lowering the
liquidus temperature. Hence, Al2O3 is not a good fluxing agent.

34
  MgO itself has a very high melting point. It its percentage is higher that it leads to a very
high melting temperature. The temperature could not be measured by the B-type
thermocouple as the thermocouple itself was melted.
 So some other oxides should be used as a fluxing agent to get a lower liquidus
Temperature in addition of these oxides.

5.5.5. CaO-Al2O3-SiO2-MgO Slag system

Table 6: Liquidus temperature for quaternary composition of CaO-Al2O3-SiO2-MgO slag system

Components Composition Thermocouple Liquidus Temperature

S. No
(in slag) (wt. % ) reading (mV) (0C)
CaO 45
Al2O3 15
1. 16.8 1460
SiO2 30
MgO 10
CaO 40
Al2O3 20
2. 17.7 1520
SiO2 30
MgO 10
CaO 40
Al2O3 25
3. 18.2 1560
SiO2 30
MgO 5

35
 CaO-Al2O3-SiO2-MgO
1580 1560
1560
Liquidus Temperature (0C)

1540 1520
1520
1500
1480 1460
1460
1440
1420
1400
MgO = 10% MgO = 10% MgO = 5%
SiO2 = 30% SiO2 = 30% SiO2 = 30%
Al2O3 = 15% Al2O3 = 20% Al2O3 = 25%
CaO = 45% CaO = 40% CaO = 40%
Slag Composition

The following interpretations can be made out of the above table:

 As the alumina content increases, the liquidus temperature increase. Therefore, to get a
lower liquidus, the alumina percentage has to be lower.
 Since the MgO percentage is very less so its impact on liquidus temperature is very less
and hence can be ignored.
 Nevertheless, since MgO saturation is required to protect the refractory lining hence it
has to lower as low as 8%.

36
5.5.6. CaO-Al2O3-SiO2-MgO-CaF2 Slag system

Table 7: Liquidus temperature for CaO-Al2O3-SiO2-MgO-CaF2 slag system

Components Composition Thermocouple Liquidus

S. No
(in slag) (wt. % ) reading (mV) Temperature (0C)
CaO 42
Al2O3 10
1. SiO2 38 16.2 1410
MgO 8
CaF2 2
CaO 37
Al2O3 10
2. SiO2 37 13.6 1210
MgO 8
CaF2 8

CaO-Al2O3-SiO2-MgO-CaF2 Comparision of liquidus

1450 temperature with and without CaF2
Liquidus temperature 0C

1400
2000
1350
Liquidus temperature 0C

1300
1250 1500
1200
1150 1000
1100
CaF2 = 2% CaF2 = 8% 500

MgO = 8% MgO = 8% 0
SiO2 = 38% SiO2 = 37% 1 2 3
Axis Title
Al2O3 = 10% Al2O3 = 10%
CaO = 42% Average CaO = 37% CaO-SiO2-Al2O3-MgO
Composition CaO-SiO2-Al2O3-MgO-CaF2

37
DTA Analysis of CaO-Al2O3-SiO2-MgO-CaF2 Slag system

 The above graph suggest the Differential Thermal Analysis where it can be clearly seen the
dip at 1180 0C for red graph, and at 1390 0C for black graph.
 Red graph is for fluorspar rich slag and Black line has negligible amount of fluorspar.
 The lowest liquidus temperature found with CaO-Al2O3-SiO2-MgO-CaF2 system with
fluorspar addition is around 1200 0C and the lowest liquidus achieved without fluorspar
addition can be around 1400 0C.

38
6. Summary and Conclusions
As far as the technical aspects are concerned, we got a better understanding of the behaviour of
fluorspar with different component in the slag. The presence of fluorspar in the slag decreases
the liquidus temperature of the slag. Because of this, the viscosity of slag gets reduced which
increases the solubility of various slag components. Higher solubility of CaO, which is the major
component in the slag components, is helpful in enhancing better desulphurization process. On
the other hand, if the fluidity is too much high, then the slag reacts with the refractory wall
resulting into erosion of refractory. Therefore, the fluidity of the slag has to be optimized so that
the slag has desired interaction with the melt and that it does not damage the refractory. The
CaF2 percentage in the slag is directly responsible for the refractory damage as it penetrates the
dolomite based refractory wall by dissolving the major component of the refractory (MgO) into
the slag. Hence using fluorspar as a fluxing agent in ladle furnace erodes refractory. It also has
adverse environmental effects.
Without fluorspar addition, the liquidus temperature of the slag is relatively higher than that of
the slag without fluorspar additions. Pure oxide has very high melting temperature, if the slag
has two components; the liquidus temperature is somehow less but is still very high for the
secondary steelmaking process. However if the slag has three components then even lower
liquidus temperature is achieved and if the slag has four components then further lower liquidus
temperature is achieved.
For CaO-SiO2 system, lowest liquidus achieved is 1440 0C. For CaO-Al2O3 lowest liquidus achieved
is 1420 0C. This suggest that slag containing high Silica content have higher liquidus temperature.
However, for the CaO-MgO-SiO2 system, lowest liquidus is less than that for CaO-MgO-Al2O3
system liquidus temperature. This suggests that slag containing Silica has lower liquidus
temperature than the slag containing Alumina but this is true for ternary system. For the
quaternary slag system, containing CaO-MgO-SiO2-Al2O3 has even lower liquidus temperature.
The liquidus temperature in this quaternary slag system, slag having high silica: alumina ratio has
lower liquidus temperature than the slag having high alumina: silica ratio.

39
While looking into the alternative slag compositions, certain properties of the slag must be
maintained. Since high basicity of slag is required for the desulphurization process so CaO is
required in, high percentage as the optical basicity of CaO is maximum and hence the sulphide
capacity of CaO based slags is greater. So the percentage of CaO has is kept highest. Slag must
also contain sufficient amount of MgO so that the slag becomes sufficiently saturated with MgO
and it does not dissolve the MgO in the refractory.
45% of CaO is sufficient to get the desired basicity of the slag. Having 8% of MgO is sufficient in
attaining the saturation. The rest is SiO2 and Al2O3. Depending on the grade of steel, their
composition is varied. FeOx and other oxides are not that must significant for getting a lower
liquidus temperature, as their composition in the slag is very less.

Without fluorspar addition the liquidus temperature of the slag is relatively higher that to the
slag without fluorspar additions.

To get slag having lower liquidus temperature without using fluorspar:

 45% of CaO is sufficient to get the desired basicity of the slag.
 Having 8% of MgO is sufficient in attaining the saturation.
 The rest is SiO2 and Al2O3. Depending on the grade of steel, their composition is varied.
 Lower liquidus can be achieved for CaO-MgO-SiO2 than that for CaO-MgO-Al2O3 system.
 37% SiO2 and 10% Al2O3 has the lowest liquidus temperature.
 The lowest liquidus temperature achieved is 1410 0C.

40
7. References

[1] A. Ghosh and A. Chatterjee: “Ironmaking and Steel Making: Theory and practice” PHI
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