Slag, Steel, Ladle and Non-Metallic Inclusions Equilibria in An ASEA-SKF Ladle Furnace

Slag, Steel, Ladle and Non-metallic
Inclusions Equilibria in an ASEA-SKF

Ladle Furnace
Kamrooz Riyahimalayeri
Doctoral Thesis
Department of Materials Science and Engineering
School of Industrial Engineering and Management
KTH Royal Institute of Technology
Stockholm, Sweden, 2012
Slag, Steel, Ladle and Non-metallic Inclusions Equilibria in an ASEA-SKF

Ladle Furnace
Kamrooz Riyahimalayeri
Department of Materials Science and Engineering

School of Industrial Engineering and Management
KTH Royal Institute of Technology
SE-100 44 Stockholm
Sweden
Akademisk avhandling som med tillstnd av Kungliga Tekniska hgskolan framlgges till
offentlig granskning fr avlggande av doktorsexamen fredagen den 5 oktober, 2012 kl.
13.15 i sal B2, Brinellvgen 23, Materialvetenskap, Kungliga Tekniska hgskolan,
Stockholm. Fakultetsopponent r Dr Johan Bjrkvall, Swerea MEFOS, Lule, Sverige.
ISRN KTH/MSE--12/24--SE+ THERM/AVH

ISBN 978-91-7501-489-0
II
ABSTRACT
This study explores the possibility of prediction and modification of some of
the physicochemical properties of non-metallic inclusions by considering
top slag-steel-ladle equilibria in an ASEA-SKF ladle furnace.
To test the reliability of an available computational thermodynamic
computer program, the first sub project was done. It was concluded that
LiMeS, an interface for Thermo-Calc, is a useful tool for slag-steel
equilibrium calculations.
The second sub project was set out to find some model/s that could
calculate the most accurate oxygen activity of molten steel compared to the
measured one. This study concluded that both Wagners and Turkdogan's
equations are useful. It was further seen that increasing the Al contents in
the molten steel, increasing the CaO/Al2O3 ratio in the top slag, and
reducing the temperature, resulted in reduction of the oxygen activity of the
molten steel.
In the third sub project a comparison was made between measured CaO
and Al2O3 (normalised to CaO-Al2O3) in top slag, calcium aluminate
inclusions, and the results of theoretical calculations. The average contents
of CaO and Al2O3 in all inclusions were close to the composition of the phase
Ca12Al14O33 and the contents of CaO and Al2O3 in the slags were close to the
composition of the phase Ca3Al2O6 in the binary phase diagram of CaOAl2O3.
The forth sub project set out to study the effect of vacuum degassing time
on non-metallic inclusions. It was concluded that during the vacuum
degassing process the share of calcium aluminates compared to spinels, Ca
content of the oxides, and the average equivalent circle diameters of the
oxides were increasing, and oxides tended to form spherical shapes.
Finally, based on the preceding four sub projects, the fifth sub project aimed
to optimize the steel treatment in an ASEA-SKF ladle furnace. The final
results showed that by adding 200 kg fluorite to the top slag of 1200 kg, it
was possible to achieve a sulphur content of less than 10 ppm in the steel
and a sulphur ratio between slag and steel of 1570, and at the same time
reduce the oxygen activity of the molten steel and the degassing time.
Keywords: Clean steel; Top slag; Non-Metallic Inclusions; Oxides; Vacuum
Degassing; Deoxidation; Desulphurization; Equilibrium; Computational
Thermodynamics; Scanning electron microscopy.
III
IV
Non-metallic inclusions in SEM
VI
ACKNOWLEDGMENTS
This industrial PhD work was carried out at the R&D department of Ovako
Hofors AB in Sweden. In order to accomplish my thesis work, I was
honoured to be in daily contact with my good friends and colleagues at
different departments of Ovako Hofors AB, and the Royal University of
Technology (KTH); all of them deserve to be thanked.
In R&D department of Ovako, I would like to express my sincere gratitude
and appreciation to Patrik lund, my industrial supervisor for his support,
openness, and understanding, Garry Wicks for his valuable guidance about
operating SEM and evaluating the results, Jan-Erik Andersson for our
discussions, Jarl Mrtenson for his support, and all other friends and
colleagues who have assisted me to accomplish my job.
I am very grateful to my academic supervisor at KTH, Professor Malin
Selleby for her great endorsement, constructive guidance and assistance
during my work. I have learnt a lot from her, especially in the field of
computational thermodynamics.
In production plant of Ovako, I would like to express my sincere gratitude
to Sven-Olof Ericsson, Dr. Robert Eriksson, Fredrik Boman, and Petter
Persson for their assistance during different parts of this project.
I would like to thank Thermo-Calc Software AB for preparing Thermo-Calc
and LiMeS for my PhD work.
I do appreciate all anonymous reviewers comments and suggestions about
my published papers; I learned a lot from them.
Christopher Fallqvist, Johan Borg, Stefan Akterhag, Joakim Fagerlund, Patrik
Holm, Christer Malmquist, Britt-Marie Johansson, Ove Grelsson, Jan A.
Pettersson, and Pernilla Sellfors-Forsling are kindly thanked.
My greatest appreciation goes to my parents Minoo and Hosein, my
brothers Kaveh and Peyman with their family, and most of all to my wife
Anna for all support, understanding and encouragements.
Thank you all.
Kamrooz Riyahi
Gothenburg, Sweden, September 2012
VII
VIII
SUPPLEMENTS
This thesis is based on the following supplements:
1- Slag-Steel Equilibrium Calculations by Computational Thermodynamics:

Comparison with the Plant Data
K. Riyahimalayeri, P. lund, M. Selleby
Published in the proceeding of the International Symposium on Liquid Metal
Processing and Casting (LMPC 2011)
pp 127-134 September 25-28, 2011, Nancy, France.
2- Oxygen activity calculations of molten steel: comparison with measured results
Published online in Steel Research International Journal; accepted on 6th Jul
2012
DOI: 10.1002/srin.201200114
3- Comparison between measured CaO and Al2O3 normalised to CaO-Al2O3 in top slag,
calcium aluminate inclusions, and results of theoretical calculations
Published online in Ironmaking & Steelmaking Journal; accepted on 6th May
2012
DOI: 10.1179/1743281212Y.0000000046
4- Development of oxide inclusions during vacuum degassing process
K. Riyahimalayeri, P. lund
Published online in Ironmaking & Steelmaking Journal; accepted on 17th May
2012
DOI: 10.1179/1743281212Y.0000000049
5- Top slag optimization in an ASEA-SKF ladle furnace
Published in the proceeding of the Richard J. Fruehan Symposium: Physical
Chemistry of Sustainable Metals
pp 311-320, June 1-2, 2011, Pittsburgh, PA, USA.
Other related publication prepared during the doctoral project, but not included in the
thesis:
6- Non-metallic inclusions during vacuum degassing process in an ASEA-SKF ladle
furnace
Published online in Ironmaking & Steelmaking Journal; accepted on 18th Jul 2012
DOI: 10.1179/030192312X13456346122543
IX
Authors contributions to each supplement:

1- Project planning, literature survey, Thermo-Calc & LiMeS
computations, some plant trials, data analysis, and writing the article
(article was edited by Prof. M. Selleby).
2- Project planning, literature survey, Thermo-Calc computations
(partly by Prof. M. Selleby), theoretical thermodynamic calculations,
SEM analysis of non-metallic inclusions, some plant trials, data
analysis, and writing the article (article was edited by Prof. M.
Selleby).
3- Project planning, literature survey, theoretical calculations, SEM
analysis of non-metallic inclusions, some plant trials, data analysis,
and writing the article (article was edited by Prof. M. Selleby).
4- Project planning, literature survey, SEM analysis of non-metallic
inclusions, data analysis, and writing the article.
5- Project planning, literature survey, LiMeS computations, some plant
trials, data analysis, and writing the article (article was edited by Prof.
M. Selleby).
6- Project planning, literature survey, theoretical thermodynamic
calculations, SEM analysis of non-metallic inclusions, data analysis,
and writing the article.
Parts of this work have been presented at the following conferences:
1- Slag-Steel
Equilibrium
Calculations
by
Computational
Thermodynamics: Comparison with the Plant Data
Presented at the International Symposium on Liquid Metal Processing
and Casting (LMPC 2011)
September 25-28, 2011, Nancy, France.
2- Top slag optimization in an ASEA-SKF ladle furnace

Presented at the Richard J. Fruehan Symposium: Physical Chemistry
of Sustainable Metals
June 1-2, 2011, Pittsburgh, PA, USA.
3- Equilibrium calculations of Slag-Steel in an ASEA-SKF ladle furnace

Accepted for presentation at the 4th International Conference on
Process Development in Iron and Steelmaking (Scanmet IV)
June 10-13, 2012, Lule, Sweden.
XI
XII
TABLE OF CONTENTS
1. Introduction...........................................................................................................................1
2. Theoretical background....................................................................................................7
2.1. Computational thermodynamics ..........................................................................8
2.2. Sulphur removal...........................................................................................................9
2.3. Oxygen removal............................................................................................................9
2.4. Oxygen activity calculations................................................................................. 10
2.5. Non-metallic inclusions ......................................................................................... 12
2.6. Removal of non-metallic inclusions.................................................................. 16
3. Experimental ...................................................................................................................... 19
3.1. Steel melting plant of Ovako Hofors AB.......................................................... 19
3.2. Sample analyzing methods................................................................................... 20
3.2.1. Steel and slag....................................................................................................... 20
3.2.2. Oxygen activity ................................................................................................... 20
3.2.3. Scanning electron microscopy..................................................................... 20
4. Results................................................................................................................................... 21
4.1. Results of supplement 1 ........................................................................................ 21
5. Discussion............................................................................................................................ 45
6. Summary of conclusions................................................................................................ 49
7. Suggestions for future works ...................................................................................... 51
8. References ........................................................................................................................... 53
XIII
XIV
1. INTRODUCTION
Non-metallic inclusions are naturally occurring and typically undesired
products that are formed into various types depending on their favourable
thermodynamic conditions in almost all treatment practices involving
molten steels.
Apart from some applications where inclusions are supposed to be
demanded, like sulphides for improving machinability (that could be
argued with recently available cutting machines and tools), they usually
deteriorate mechanical properties and surface quality of steel products and
could cause nozzle clogging and disruption of steelmaking and forming
processes.
It is widely believed that due to the presence of sulphide and oxide
inclusions some of the mechanical properties of steels like ductility,
toughness, anisotropy, and formability might be negatively affected [1].
One of the ongoing demands at Ovako Hofors AB is to reduce sulphur and
total oxygen (TO) content of bearing steels. Regarding sulphur and TO
contents of bearing steels, it is believed that under cyclic loadings, sulphide
and oxide inclusions can act as crack initiators resulting in fatigue failure
and life reduction of bearing components [1].
The harmful effects of non-metallic inclusions on fatigue properties of steel
parts are because they can act as potential sites of stress concentration that
can initiate cracks under cyclic loadings.
Fig. 1 presents the relation between fatigue life of ball bearing versus
number of oxide inclusions larger than 30 m [2]. From this figure it is clear
that the presence of more oxides, especially larger ones, could have very
devastating effect on the fatigue life of ball bearings.
Figure 1: Fatigue life of ball bearings versus number of oxide inclusions larger
than 30 m [2].
Harmful effects of non-metallic inclusions are highly dependent on their

chemical compositions, volume fractions, dispersions and morphologies [35]. Generally large and unbreakable inclusions with high melting points are
the most unwanted ones; however compared to these inclusions, small and
breakable ones or those with lower melting points are more preferred
[4,6,7]. The reason for these preferences is that inclusions that have lower
melting points or are breakable are likely to be deformed, crushed to
smaller inclusions, or disappeared in following hot or cold forming
processes (effect of forming process and reduction ratio) or heat treatments
that steels might have after teeming and solidification process.
Negative effects of non-metallic inclusions on fatigue properties of steels
seem to be especially more pronounced in steels with higher tensile
strength, i.e. steels with lower strength may fail under cyclic loadings due to
matrix related reasons.
In most of the secondary metallurgical treatment plants of steelmaking
companies, slag, steel and ladle are involved. Thus the composition of slag,
steel, and ladle are very crucial factors for reaching the desired final steel
properties, and they have crucial effects on chemical compositions, volume
fractions, dispersions and morphologies of non-metallic inclusions. Fig. 2
presents some of the most important factors that could affect
physicochemical properties of inclusions.
Figure 2: Some of the most important factors that could affect chemical
composition, volume fraction, dispersion and morphology of inclusions during
steelmaking process.
This PhD work set out to study some of the most important factors that
could affect physicochemical and statistical properties of non-metallic
inclusions in bearing steels during vacuum degassing. In order to achieve
this task several sub projects and activities were set. These sub projects
were presented in five supplements that are the bases of this PhD work.
The specific goals of these supplements are shown in Fig. 3. The brief
outcomes of these supplements are presented in the result part of this
report.
3
Figure 3: General overview of five supplements and their respective objectives.
Figure 4: Logic behind the project and each supplement.
Fig. 4 shows the logic behind different supplements of this project. This
project started with a pre-study regarding steel desulphurization [8-18],
steel deoxidation [19-55], and removal of non-metallic inclusions [56-87].
These studies implied that in order to study the important factors that
affect compositions, volume fraction, dispersion, and morphologies of nonmetallic inclusions both thermodynamic and kinetic aspects of steelmaking
should be considered.
In order to check the reliability of an available computational
thermodynamic computer program, the first sub project was performed
(explained in supplement 1); results of this supplement suggested that by
considering tolerances of the process, apart from oxygen level of the molten
steel that is a very crucial component for this study and is required to be
predicted with very high accuracy, other components in top slag and steel
could be calculated with acceptable (for this project) error.
The second sub project set out to find some model/s that could calculate
the closest oxygen activity of molten steel to the measured oxygen activity
in an ASEA-SKF ladle furnace (explained in the supplement 2).
The third sub project that was explained in supplement 3 set out to study
the possible relations between Ca and Al in oxide inclusions, top slag, and
the results of theoretical calculations.
The forth sub project that was explained in supplement 4 set out to study
the effect of vacuum degassing time on development of non-metallic
inclusions.
Finally, based on all these four sub projects, the fifth sub project with the
aim of optimization of steel treatment in an ASEA-SKF ladle furnace was
performed (explained in the supplement 5).
A brief summary of all these supplements are presented in the result part of
this report and all supplements in their pre-published format are attached
to the end of this report.
The sixth sub project was a continuation and complement for supplement 4.
This supplement is also attached to the end of this report but is not
explained in this thesis work.
2. THEORETICAL BACKGROUND
Vacuum degassing process in the ASEA-SKF ladle furnace of Ovako was
chosen as the main pillar of this project. Vacuum degassing could be
considered as one of the most crucial stages of steelmaking and ladle
treatment process; this is because at the end of this stage final chemical
composition, deoxidation, desulphurization, and inclusion removal should
be achieved.
Degassing process, with help of proper top slag-steel stirring and top slag
choice is supposed to contribute positively to removal of unwanted nonmetallic inclusions as much as possible and result in a cleaner and more
homogeneous steel melt; however at the moment it is difficult to predict the
optimized thermodynamic and kinetic conditions of the vacuum degassing
process that would result in the most favourable and optimized treatment
conditions.
Usually after finishing vacuum degassing due to lack of enough slag-steel
stirring and possibility of adding any extra material, it is not easy to make
any changes to the system; consequently morphology, volume fraction,
composition, and dispersions of non-metallic inclusions at the end of the
vacuum degassing process could not easily be changed (any possible effects
of casting powder in the moulds and mould linings during teeming and
solidification are not considered).
Traditional ways to study the effects of various parameters on non-metallic
inclusions are performing experimental tests in both production plant and
laboratory scales; however these experiments are usually expensive, timeconsuming and sometimes even impossible to perform. But, in order to
reduce the necessary experiments in the design of new materials,
improvement of existing materials, and controlling as well as developing
metallurgical processes, computational thermodynamics may be applied
[88].
In this project it was tried to contribute to the knowledge of steelmaking
and ladle treatment by applying computational thermodynamics, plant
experiments and comparing these results with each other in order to
achieve a practical understanding regarding morphology, volume fraction,
dispersion, composition, and development of non-metallic inclusions in the

ASEA-SKF ladle furnace.
2.1. COMPUTATIONAL THERMODYNAMICS

By means of thermodynamic properties of individual components in a
system it is possible to compute equilibrium states of the whole system.
Gibbs introduced the possibility of calculating equilibrium states of
different phases by having the thermodynamic properties of these phases
or individual elements in respective systems [89]. Kaufman and Bernstein
[90] took advantage of thermodynamic properties and developed the
CALPHAD [91-93] method that allows the calculation of phase diagrams by
means of available thermodynamic properties.
In CALPHAD computational thermodynamic calculations [91-93], or
computer coupling of phase diagrams and thermochemistry, by means of
Gibbs energy, thermodynamic properties are modelled. The minimization of
Gibbs energy is the key to the CALPHAD method, and this is due to the fact
that the Gibbs energy is a function of both temperature and pressure, and as
soon as it is calculated other thermodynamic quantities such as entropy and
enthalpy could be derived [93,94].
In recent years computational thermodynamics has had an enormous
progress [94]; several different computer programs have been developed
and are constantly improving their precision and reliability. By means of
these computer programs it may be possible to simulate, predict and
optimize different metallurgical processes; i.e. by considering different
affecting factors as constant, try to understand the effect of one or some
other desired factors in a thermodynamic system.
In some parts of this study Thermo-Calc (databases TCFE7 and SLAG3 were
used) and LiMeS [88,95] computer programs were applied to simulate the
slag-steel equilibrium in an ASEA-SKF ladle treatment furnace.
2.2. SULPHUR REMOVAL

Equations (1) and (2) are respectively believed to describe sulphur removal
reaction and sulphur distribution ratio between top slag and molten steel
during the vacuum degassing process [96]. In these equations parenthesis
represent (wt%) of component in top slag, and brackets represent [wt%] of
components in molten steel. ''ai'' denotes the activity of component ''i''.
By considering equations (1) and (2), it can be concluded that by increasing
activity of CaO, and increasing the Al amount in the molten steel, sulphur
distribution ratio between slag and steel or (S)/[S] ratio could increase.
Although more CaO seems to be very positive, it is believed that after
reaching a certain amount of CaO, any further addition of that could
decrease the (S)/[S] ratio [96]; this reduction of the (S)/[S] ratio is believed
to be due to increasing amount of unmelted CaO in the top slag that could
result in increasing the melting point of the top slag or lowering its CaO
activity, or appearance of additional heterogeneous and solid phases in the
top slag [96].
[ S ] + (CaO ) + 2 [ Al ] (CaS ) + 1 ( Al 2 O3 )
3
3
(1)
2
(S )
a(CaO )
= K [ Al ] 3 1
[S ]
a 3 ( Al2O3 )
(2)
2.3. OXYGEN REMOVAL

Active oxygen that is present in molten steel could react with strong
deoxidizers like Ca, Al, and Si that are present in molten steel. These
reactions (3) to (5) could result in reduction of oxygen activity of molten
steel as well as generation of oxide inclusions.
[Si] + 2[O] SiO2 (s)
G 0 = 581,900 + 221.8T [J/Mol]
(3) [29]
2[Al ] + 3[O ] Al2O3 (s)
G 0 = 1,202,000 + 386.3T [J/Mol]
(4) [29]
[Ca] + [O] CaO (s)
G 0 = 645,200 + 148.7T [J/Mol]
(5) [29]
Each of these elements reduces the oxygen content of molten steel to a

certain level. Reduction of oxygen activity does not necessarily result in
lower TO, however by having proper slag-steel stirring, and proper choice
of a synthetic top slag that could absorb and dissolve non-metallic
inclusions, lower TO might be achieved.
2.4. OXYGEN ACTIVITY CALCULATIONS

In this study in order to calculate oxygen activity of molten steel two
equations, Wagner's equation (10) [3] and Turkdogan's equation (14) [97]
and one computer program (Thermo-Calc [95] with databases TCFE7 and
SLAG3) were applied.
Wagner's equation: By considering equations (6) and (7), it would be
possible to apply equations (8) to (10) to calculate theoretical oxygen
activities of molten steel that is supposed to be in equilibrium with top slag.
Equation (9) is from Henry's law, and equation (10) is called Wagner's
equation.
2[ Al ] + 3[O ] Al2O3 (s)
(6)
G 0 = 1,202,000 + 386.3T j/mol
(7)
Al O
G o = RT ln 2 2 33
Al O
(8)
Al = f Al [wt % Al ]
(9)
log f Al = eAlj [wt % j]
(10)
[3,98]
Al2O3 activities that were required for solving equation (8) were calculated
by applying three different models and two different constants that were
explained in supplement 2 of this study. In order to solve equation (10),
interaction coefficient parameters [98] that are shown in Table 1 were
applied.
10
Table 1: Interaction coefficient parameters that were applied in this study [98].
j
C
Si
Mn
S
Cr
Al
O
Interaction parameters
eAl
eO
0.091
-0.436
0.056
-0.131
0
-0.021
0.03
-0.133
0.012
-0.0459
63/T+0.011
-20,600/T+7.15
-34,740/T+11.95
-1,750/T+0.734
Turkdogan's equation [97]: Equation (14) is a simplified way to present

Wagner's equation (10) and in this study is called Turkdogan's equation. By
means of equations (12) to (14), it is possible to calculate oxygen activities
of molten steel.
Equation (13) is presented by Turkdogan and is supposed to give the most
comparable result to the oxygen activities that are measured in molten steel
at production plants. This equation (13) is believed to consider a correction
factor for partial electronic conductions of the MgO-stabilized sensors; this
is more explained in supplement 2 of this study. Equation (14) is valid at
low aluminium contents [97]: f Al 1
Al2O3 2[Al ] + 3[O ]
(11)
[% Al]2 [ ppmOfO ]3
Al2O3
(12)
K=
log K =
62,680
+ 32.54
T
log f O = 3.98[% Al ]
(13) [97]
(14) [97]
Al2O3 activities that were required for solving equation (12) were
calculated from one model and one constant (0.064) that were explained in
the supplement number 2 of this study.
11
2.5. NON-METALLIC INCLUSIONS

Traditionally non-metallic inclusions have been divided into four types
(type A: Sulphides, type B: Aluminates, type C: Silicates, and type D:
globular Oxides); however because these classifications were designed to
be simple, they were not detailed enough for the purpose of this research
work; thus it was decided to apply scanning electron microscope (SEM)
with different costume defined classifications for analysing and
classification of non-metallic inclusions.
By regarding the heats that were considered in this study it was seen that
most of oxide inclusions that were formed in steel grade SAE 52100 in
ASEA-SKF ladle treatment furnace, could roughly be classified into two
main populations. These two types of inclusions are called spinel
((MgAl)xOy) and calcium aluminate ((Ca-Al-Mg)x(O-S)y); Chemical
compositions (wt% normalized to Al2O3-CaO-MgO) and typical equivalent
circle diameters (ECD in m) of some of these spinels and calcium
aluminates are shown in Fig. 5.
Figure 5: Chemical compositions (normalized to ACM) and typical ECDs (m) of

some of the observed spinels and calcium aluminates.
12
Figs. 6 and 7 show two different examples of SEM-EDS mapping analysis of

these two main types of observed oxide inclusions. Fig. 6 shows two
calcium aluminates and Fig. 7 shows two spinels (In these figures darker
areas are those parts of the inclusions that respective elements exist).
A)
B)
Figure 6: SEM-EDS mapping analysis of two calcium aluminates.
13
A)
B)
Figure 7: SEM-EDS mapping analysis of two spinels.
14
It should be mentioned that at the beginning of the vacuum degassing

process and exactly after addition of aluminium containing deoxidizers into
the molten steel, some aluminium rich oxides (alumina inclusions) could be
observed. But some minutes after addition of aluminium containing
deoxidizers, because of the thermodynamic conditions of the slag-steelladle system, and very low oxygen and sulphur levels of the molten steel,
complex inclusions that were either Al and Mg rich spinels (Mg came from
remaining EAF top slag after skimming, synthetic top slag, and ladle lining
bricks that were made of MgO-C materials), or Ca and Al rich calcium
aluminates (Ca came from synthetic top slag or added Ca as Ca-Si) tended to
form; consequently spinel and calcium aluminate inclusions were the most
abundant types of inclusions that could be observed.
In addition, because the amount of silica (SiO2) in the synthetic top slags
that were used in the production plant were always very low (less than 8
wt%), and due to the presence of deoxidizers that had higher oxygen
affinity compared to Si in the system (i.e. Al, Ca and Mg), in non-metallic
inclusions that were considered in this work, very low amount of silicon
were observed; consequently silicate inclusions were not considered in this
work.
Regarding sulphide inclusions due to thermodynamic preferences, and
because most of the samples of this study were taken from molten steel and
were chilled very quickly in a short period of time, sulphide inclusions did
not have much time and favourable thermodynamic conditions to form (at
least not as much as normal situation when steel ingots were left inside
moulds for several hours in the production plant in order to be solidified
and cooled); that was the reason that sulphide inclusions were not
considered in this work. It should be mentioned that because Ca-treatment
was not the focus of this study none of the heats that were considered in
this study were Ca-treated, however Ca-treatment of molten steel is known
to be a very effective way to make low melting point calcium aluminate and
calcium sulphide complex inclusions; this would result in isotropic
spherical non-metallic inclusions and ease the removal of unmelted Al-Mg
rich inclusions.
15
2.6. REMOVAL OF NON-METALLIC INCLUSIONS

Theoretically it is known that removal of non-metallic inclusions from
molten steel could be achieved by means of several different mechanisms.
1- According to Stokes law, equation (15), because of differences
between densities of non-metallic inclusions and molten steel,
flotation is a mechanism that could lead to removal of non-metallic
inclusions. It is possible to calculate theoretically the rate of inclusion
removal due to flotation by means of equations (15) and (16) [61].
S=
f (r )vdt
L
(15) [61]
v=
2g
r 2
9
(16) [61]
S: Rate of inclusion removal due to flotation

r: Radius of non-metallic inclusions
L: Depth of molten steel in ladle
v: Terminal velocity of non-metallic inclusions in molten steel
g: Gravity acceleration
: Viscosity of molten steel
: Mass density difference between inclusions and molten steel
2- Magnetic stirring and argon gas injection can improve the removal of
non-metallic inclusions. Rate of non-metallic inclusions entrapment
by means of argon gas injection is presented by equation (17) [61].
Sb = Nbvb
b2
V
(17) [61]
Sb: Rate of non-metallic inclusions entrapment

Nb: Number of bubbles
vb: Difference between velocities of molten steel and bubble
b: Critical entrapment distance
V: Volume of molten steel
16
3- Ca-treatment is another effective way that could facilitate the removal

of non-metallic inclusions from molten steel. By adding Ca to the
molten steel (mostly in form of Ca-Si), it is possible to modify
unmelted Al-Mg rich inclusions (spinels) to large, isotropic, and
spherical calcium aluminates and calcium sulphides with low melting
points; this would ease the removal of molten non-metallic inclusions.
It should be mentioned that it might become a problem if for any
reasons some of these large calcium aluminates remain or get
trapped in molten steel.
4- Optimized top slag properties can enhance the inclusions removal in
a ladle furnace. The three mechanisms mentioned above could be
used in order to understand inclusions movement from the middle or
bottom parts of the molten steel or ladle to the top; however without
a proper top slag, it is highly probably that these inclusions could not
be removed efficiently. Consequently, in order to ensure a very
effective entrapment and absorption of non-metallic inclusions by
means of top slag, having an optimized molten top slag with high
capacity for non-metallic inclusions (for example high alumina
capacity), proper wetting properties and viscosity is necessary.
17
18
3. EXPERIMENTAL
3.1. STEEL MELTING PLANT OF OVAKO HOFORS AB
Fig. 8 presents the general schematic of the steel melting plant of Ovako
Hofors AB. Scraps are melted in the 100 t, bottom tapped electric arc
furnace, molten metal is tapped into the ASEA-SKF ladle furnace station,
then by means of ferro-silicon and ferro-aluminum the molten steel is
deoxidized (its oxygen activity is reduced), then the slag that is the result of
this deoxidation is skimmed, and the ladle filled with molten steel is sent to
the ladle treatment station.
In the ladle furnace, synthetic top slag, mainly composed of CaO and Al2O3,
is put on the molten steel, then the melt is desulphurized, deoxidized, its
alloying composition adjusted, vacuum degassed, Ar-gas and magnetic
stirred, possibly reheated, and finally after the temperature of the melt is
adjusted to the desired temperature, it is poured into 24 ingot moulds with
the capacity of 4.2 t each.
Figure 8: Schematic of the steel melting plant of Ovako Hofors AB.
19
3.2. SAMPLE ANALYZING METHODS

3.2.1. STEEL AND SLAG
Steel samples were tested by two testing instruments: OES ARL 4460 Metal
analyzer from Thermo Fisher Scientific Inc was used for metal analyses; an
instrument called Leco CS-444 was used in order to analyze sulphur and
carbon content of the samples. This instrument works based on the CarbonSulphur combustion method (ASTM E1019). An instrument called Leco
TC600 was used in order to analyze total oxygen of the samples, and all slag
samples were analyzed by an X-ray fluorescence (XRF) spectrometer
instrument called PANalytical Axios mAX- Minerals.
3.2.2. OXYGEN ACTIVITY
The Celox instrument [99] that was equipped with commercial consumable
MgO-stabilized ZrO2 electrode was applied in order to measure oxygen
activity and temperature of molten steel at the respective sampling
occasions. This instrument allows operator to measure oxygen activity and
temperature of molten steel in situ at different stages of steelmaking
process. According to the Nernst's law the difference between oxygen
activity of the electrodes and molten steel would generate an electro motive
force (EMF) and by considering this EMF it is possible to calculate oxygen
activity of molten steel.
It should be mentioned that in Al killed steels, and at low oxygen activities,
measured oxygen activities are believed to be within a factor of two higher
than the true equilibrium oxygen activities of molten steel [97]. These
higher measured oxygen activities are probably due to partial electronic
conduction of the MgO-stabilized ZrO2 electrodes in molten steel that would
result in higher EMF [97]. However some other studies have claimed that
Celox instrument applies a correction factor that is supposed to consider
this partial electronic conduction [100-103].
3.2.3. SCANNING ELECTRON MICROSCOPY
For microscopic scanning of the steel samples regarding oxide inclusions,
analytical scanning electron microscope (SEM) brand Leo Supra 35 was
applied and for the analysis and classification of non-metallic inclusions,
using energy dispersive X-ray microanalysis, INCA Feature software [104]
was used.
20
4. Results
The results of this PhD work could be divided into five different
supplements that are briefly explained in separated categories in the
following parts of this report. All five supplements are attached to the end
of this report.
4.1. RESULTS OF SUPPLEMENT 1

This study presented a comparison between the measured and the
calculated results of some slag-steel equilibria in an ASEA-SKF ladle
furnace. The new software LiMeS [88,95] available with the Thermo-Calc
software package was applied in order to calculate the slag-steel
equilibrium after the vacuum degassing process. The input data used in the
calculations were those achieved by instrumental analysis of the slag-steel
samples that were taken before starting the vacuum degassing process.
Finally the calculated results were compared with the measured values.
Fig. 9 shows the calculated results by LiMeS [88,95] versus the measured
results achieved by instrumental analysis. In the legends of this figure
parenthesis represent (wt%) component in slag, and brackets represent
[wt%] of components in molten steel. By considering the fact that results
achieved by instrumental analysis could have some errors, some important
results that were achieved from this supplement could be summarized as
below:
Regarding the contents of Al, Mn and Si in molten steels and the
amount of the Al2O3 and SiO2 in the top slag the calculated results
were in a quiet good agreement with the measured results.
Considering the calculated oxygen activity, S and Mg contents in the
molten steel, and S, MgO, and CaO contents of the slag, they disagree
with the measured ones.
Disagreement between the measured and the calculated results of the
Mg and its oxide was believed to be due to the fact that MgO-C ladle
lining bricks continuously contributed some amount of Mg to the
steel melt.
21
One of the reasons for the deviation between the measured and the
calculated oxygen content of the molten steel could be that the slagsteel system was unintentionally allowed to react with the
surroundings during the vacuum degassing process.
The deviations of the calculated Al contents in the molten steel
compared with the measured results could also be explained by the
hypothesis that some oxygen was continuously added to the system
and consumed Al of the molten steel, and generated some amount of
Al2O3.
Thermodynamic calculations (here using LiMeS [88,95]) were very
useful tools when studying e.g. slag-steel systems in ladle treatment
plants. The only inputs needed were temperature, pressure and
starting material. It should be mentioned that for non regular
Thermo-Calc users, using LiMeS [88,95] is much simpler; this would
bring the opportunity of taking advantage of this software in a wide
areas of applications also for non regular users.
22
Figure 9: Values calculated by LiMeS [88,95] versus the measured values. (%wt)
and [%wt] respectively denote the amount of the components in top slag and
molten steel.
23

This study set out to find some model/s that could calculate the closest
oxygen activity of molten steel to the measured oxygen activity in an ASEASKF ladle furnace. Ten steel heats grade SAE 52100 were chosen, oxygen
activities of the molten steel after vacuum degassing process were
measured, then by means of two different equations (Wagner's equation
(10) [3] and Turkdogan's equation (14) [97]) and one computer program
(Thermo-Calc [95] with databases TCFE7 and SLAG3) the theoretical
oxygen activities were calculated and compared to the measured results.
Four different models: Ohta-Suito [105], Chipman [106], Tanabe [107],
IRSID [108,109] and two different constants: 1 and 0.064 were applied in
order to calculate the respective Al2O3 activities that were applied for
calculating oxygen activities.
Fig. 10 shows the calculated and measured amounts of oxygen in molten
steel of the ten test heats that were considered in this work.
Figure 10: The calculated and measured oxygen activities of the ten different test
heats.
24
Fig. 11 shows three models that resulted in the closest calculated oxygen
activities among all different applied models versus the amount of the
measured oxygen activities.
Fig. 12 shows the possible changes in oxygen activities of molten steel
depending on wt% Al in molten steel, temperature of equilibrium, and
respective CaO/Al2O3 ratios in the top slag that were normalised to the
binary system of CaO-Al2O3. Oxygen activities on this figure were calculated
by means of Turkdogan's equation (14), and Al2O3 activities were calculated
from Chipmans results [106]. Fig. 12 is supposed to give the closest results
that are comparable to the oxygen activities that are measured by the Celox
instrument [99].
In legend parts of these figures (10 to12) and regarding the name of series,
terms before comma refer to either Wagner's equation (10) or Turkdogan's
equation (14), and the expressions after comma refer to the methods that
were applied in order to calculate the activities of Al2O3 in each calculation.
Figure 11: The closest calculated oxygen activities versus the measured ones.
25
Figure 12: O versus wt% Al at different temperatures and CaO/Al2O3 ratio.

Results should be comparable to the measured results of the Celox instrument
[99].
As a result of this supplement it was found that Equations (18) and (19)
should give the results that are comparable to the measured results of the
Celox instrument [99] respectively without and with considering the
CaO/Al2O3 ratio in the top slag.
O = 19.8 + 0.014Temp12.9[Al]
R2 = 86.7%
(18)
O = 19.9 + 0.0158Temp 4.42[Al] 0.0491(CaO)
R2 = 90.1%
(19)
Equation (19) should give the closest results comparable to the oxygen
activities that are measured by the Celox instrument [99] by considering
26
the CaO/Al2O3 ratio in the top slag; however it requires the wt% CaO of the
top slag as an input that might not always be available.
Some of the results achieved from this study could be summarized as
follow:
Both Wagner and Turkdogan's equations were useful for calculating

oxygen activities of molten steel.
Most of the oxygen activity results that were calculated theoretically

were lower than the measured results.
If the measured oxygen activities of the molten steel by means of

Celox instrument [99] are supposed to be the true oxygen activities in the
slag-steel equilibrium, it could be said that by applying Turkdogan's
equation (14), and calculating the Al2O3 activities by means of Chipman's
results, or by applying Turkdogan's equation (14), and using activities of
Al2O3 constant as 0.064, or by applying Wagner's equation (10), and using
activities of Al2O3 constant as 1 the closest calculated results compared to
the measured oxygen activities of the molten steel could be achieved.
Positive effect of Al addition to molten steel in order to reduce oxygen

activities reduced as the wt% Al in molten steel was more than 0.05.
Temperature of molten steel was an important factor that affected

oxygen activity of molten steel.
Higher ratio of CaO/Al2O3 could result in less oxygen activities of

molten steel; this could be achieved by lowering activity of Al2O3 in the top
slag.
Two regressions were generated that are supposed to be useful to

practically calculate oxygen activities of molten steel at different
temperatures, depending on wt% Al in molten steel and CaO/Al2O3 ratio in
the top slag.
The SEM observations revealed that the main types of observed nonmetallic inclusions in these samples were spinels and calcium aluminates,
and by increasing the CaO content of the inclusions their ECDs grew.
27

In this study it was investigated if there was any relation between the wt%
CaO and Al2O3 in the binary system of CaO-Al2O3 of calcium aluminates
(CaOincl and Al2O3incl ) and their amount in the top slag before teeming
(CaOslag and Al2O3slag) and the theoretically calculated wt% CaO and Al2O3
normalized to their binary system (CaOcalc and Al2O3calc). In case a certain
relation could be established it would be possible to predict compositions
and physicochemical properties of non-metallic inclusions based on the
applied top slag during ladle treatment in the desired ways.
Fig. 13 presents the CaOincl, CaOslag, and CaOcalc in all four samples of this
study, in this figure there are also two other lines indicating one standard
deviation above and one standard deviation below the average CaOincl. Fig.
14 presents the Al2O3incl, Al2O3slag, Al2O3calc in all four samples of this study, in
this figure there are also two other lines indicating one standard deviation
above and one standard deviation below the average Al2O3incl.
Figure 13: Measured and calculated CaOincl, slag, calc in all four samples of this study.
28
Figure 14: Measured and calculated Al2O3incl, slag, calc in all four samples of this
study.
Fig. 15 shows the calculated and the measured positions of the CaOincl,
CaOslag, and CaOcalc in all four samples of this study in the binary phase
diagram of CaO-Al2O3 [110]. In this figure there are also two other lines
indicating one standard deviation above and one standard deviation below
the average CaOincl in the four different samples of this study.
29
Figure 15: The calculated and the measured positions of the CaOincl, slag, calc in all
four different samples of this study, in the binary phase diagram of CaO-Al2O3
[110].
The following points briefly mention some of the achieved results of this
study.
In the calcium aluminates, Mg were often seen as spinel and Al that
did not form spinel, formed calcium aluminates with different CaOincl
and Al2O3incl ratios (the available Ca was assumed to be the rest of Ca
that had already formed CaS phase with all available S).
The CaOincl and Al2O3incl in all samples did not have the same ratio; but
they covered a large range.
The average CaOincl and Al2O3incl in all samples had nearly similar
compositions that were close to the border of the phase Ca12Al14O33 in
the binary phase diagram of CaO-Al2O3 [110].
30
The CaOslag and Al2O3slag in all samples had almost similar

compositions that were close to the border of the phase Ca3Al2O6 in
the binary phase diagram of CaO-Al2O3 [110].
The results of theoretical calculations were close to the CaOslag and
Al2O3slag, but they did not follow the same maximum and minimum
tendencies of the CaOslag and Al2O3slag.
31

This article set out to study development of oxide inclusions during the
vacuum degassing process in an ASEA-SKF ladle furnace. During the
degassing process and with about 15 minutes intervals and by means of
vacuum interruption technique, five steel samples (argon protected liquid
steel samples) and top slag samples were taken and their chemical
compositions were instrumentally analyzed. All steel samples were further
analyzed by a scanning electron microscope and the results were shown. In
this report these five samples are designated S1 to S5.
Fig. 16 shows sampling occasions of the five samples with the respective
internal pressures of the ASEA-SKF ladle furnace during the vacuum
degassing process. As could be seen the first sample was taken before
starting the degassing process and three others were taken with about 15
minutes interval from the start of the degassing, the last sample was taken
after finishing the degassing process. The entire degassing process took
about 55 minutes.
Figure 16 Pressure (torr) vs Time (min) from start of the degassing, and sampling
positions.
32
Fig. 17 shows the content of components in molten steel and top slag and
steel temperature at the five sampling occasions of this study during
vacuum degassing.
Figure 17: Changes of the amounts of components in samples and temperature

during vacuum degassing.
33
Fig. 18 shows five graphs that were drawn by INCA Feature software [104].
These graphs show the position of all of the oxides that were found and
analyzed by SEM in the five samples of this study in normalized ternary
phase diagrams of Al2O3, CaO, and MgO (CAM).
Figure 18: Oxides observed in five samples of this study.
34
Fig. 19 shows five graphs that present wt% Ca versus wt% Al in all oxides
observed by SEM, the bubble sizes present the ECDs (m) of these oxides.
Each figure is for one of the five samples of this study.
Figure 19: Wt% Ca versus wt% Al in oxides of five samples of this study, bubble
sizes show ECDs (m) of these oxides.
35
Fig. 20A) shows the percentage share of spinels and calcium aluminates of
all oxides that were achieved from SEM analysis of the five different
samples of this study and Fig. 20B) shows the percentage share of oxides
ECDs (m) in the samples. In Fig 20B) oxides, independent of their chemical
compositions, were separated into four classes. Minimum ECDs of
considered oxides were 5m. Fig. 21 shows the average ECDs (m) of
spinels and calcium aluminates of all five samples.
A)
B)
Figure 20: A) Percentage share of oxides in the five samples of this study. B)
Percentage share of oxides ECDs (m) in the five samples of this study.
36
Figure 21: Average ECDs (m) of spinel and calcium aluminates in the five samples
of this study.
Results achieved form this study could be summarized as follow:

During the vacuum degassing process:
spinels and calcium aluminates were the dominant types of

inclusions.
several factors such as temperature and top slag-steel compositions

were changing.
percentage share of calcium aluminates, compared to spinels were

increasing.
Ca weight percent content of oxides was increasing.
average ECDs of spinels were constant (around 5m).
average ECDs of calcium aluminates were increasing.
percentage share of oxides with bigger ECDs were increasing.
oxides tended to form round shapes.
TO of the samples were decreasing.
37

The aim of this study was to optimize the steelmaking process that would
result in increasing the sulphur distribution ratio between slag and steel of
synthetic top slag, reduce the oxygen activity of molten steel and reduce the
vacuum degassing time in the ASEA-SKF treatment plant of Ovako Hofors
AB.
In this paper the synthetic top slag of ASEA-SKF ladle furnace was studied
by means of thermodynamic calculations using the LiMeS software [88,95].
It was thus concluded that if fluorite was added to the synthetic top slag,
(%S)/[%S] ratio would be increased. By considering this, four plant test
heats with addition of fluorite to the top slag were performed and
compared with the 24 reference heats that had already been produced in
the same plant.
Figs. 22 to 24 were calculated by means of LiMeS [88,95]. In order to
calculate these figures the molten steel was supposed to be in equilibrium
with the top slag at constant pressure of 105 Pa. These figures present the
theoretically calculated amount of CaO (kg) in the synthetic top slag that is
supposed to be unmelted or heterogeneously dispersed as solid particles in
the top slag; these figures respectively consider the changes in the amount
of the unmelted CaO in the synthetic top slag by varying the amount of the
added CaO (kg) to the synthetic top slag, equilibrium temperature (C) of
the slag-steel, and the amount of the added fluorite (kg) to the synthetic top
slag.
Figure 22: Amount of the unmelted CaO (kg) versus amount of the CaO (kg) in the
synthetic top slag, calculated by LiMeS [88,95] at 1600C.
38
Figure 23: Amount of the unmelted CaO (kg) versus equilibrium temperature (C)
of the molten steel, calculated by LiMeS [88,95].
Figure 24: Amount of the unmelted CaO (kg) versus amount of the added fluorite
(kg) in the synthetic top slag, calculated by LiMeS [88,95] at 1600C.
39
By considering equations (1) and (2) and Figs. 22 to 24 it can be concluded

that if the CaO/Al2O3 ratio in the top slag could be increased or the mass
fraction of the CaO in the top slag could be increased, and at the same time
slag could be kept molten, it is possible to achieve higher sulphur
distribution ratio between slag and steel or higher (%S)/[%S] ratio. It could
also be said that by increasing the mass fraction of the molten or active CaO,
or reducing the melting point, or increasing the liquid fraction of the top
slag, it is possible to increase (%S)/[%S] ratio of the currently used top slag
in the ASEA-SKF ladle furnace.
By considering Fig. 25, it was clear that by addition of fluorite to the
currently used top slag in the ladle furnace it was possible to achieve higher
(%S)/[%S] ratio, yielding sulphur content as low as 10 ppm. Consequently,
compared to the normal steelmaking practices, all four test heats at the end
of the degassing process and after reheating showed lower sulphur content
in the molten steel.
Figure 25: Sulphur content (ppm) during different treatment steps of the 24
reference heats and the four fluorite added test heats.
40
Fig. 26 is a representative of SiO2 reduction by Al in the slag-steel system,

the equilibrium lines that were calculated by Thermo-Calc (databases
TCFE7 and SLAG3 were used) [95] at three different temperatures could be
applied as a tool for predicting the flow of oxygen in slag-steel system that
is supposed to be in equilibrium. By considering this graph it could be said
that by adding 200 kg fluorite to the top slag, it was possible to have lower
oxygen potential in the slag comparing with the steel, consequently it could
be concluded that oxygen in the steel had a tendency to flow toward the top
slag, and in case of other test heats that had the points after vacuum
degassing above the calculated equilibrium lines, it was likely that oxygen
flows from the top slag to the steel, and probably leads to formation of more
oxide inclusions and a less clean steel.
This graph could be used as a very useful guide for understanding the
reoxidation possibilities of molten steel from the top slag and even mould
powder during following stages of steelmaking process.
Figure 26: The ratio between the SiO2 contents (wt%) in the slag and the Si
content [wt%] in the molten steel versus Al content [wt%] in the molten steel
before and after degassing.
41
By considering Fig. 27 it could be said that in case of adding 200 kg fluorite

to the total amount of 1200 kg synthetic top slag comparing with the 24
reference heats, the magnesium content of the molten steel after reheating
or before teeming could increase. By regarding the fact that the ladle lining
material in the tested heats was composed of MgO-C bricks, this increase
was believed to be due to using high amount of fluorite in the synthetic top
slag that could lead to higher ladle erosion (probably by reducing oxygen
potential of the molten steel, but this should be studied in more details).
Figure 27: Mg content (ppm) of the 24 reference heats and four fluorite added test
heats during different treatment steps in ladle furnace.
42
By considering the achieved results the following conclusions could be

made.
By adding 200 kg fluorite to a top slag weight of 1200 kg it was possible to:
obtain the minimum sulphur content in bearing steel grade SAE

52100 that was equal to 10 ppm.
increase the sulphur distribution ratio between slag and steel during
the vacuum degassing and achieve (%S)/[%S] ratio of 1570.
have less oxygen potential in the slag compared with the steel.
Consequently it could be concluded that oxygen in the steel had a tendency
to flow toward the slag.
Compared with the 24 reference heats, by adding 200 kg fluorite to

the top slag weight of 1200 kg, at the end of the ladle metallurgy treatment
higher Mg (wt%) in the molten steel could be expected, this Mg probably
came from the erosion of the ladle lining material (possibly because of very
low oxygen potential of the molten steel that resulted in more ladle
erosion).
43
44
5. Discussion
In this study it was seen that synthetic top slag plays a very crucial role in
affecting chemical composition, volume fraction, dispersion, and
morphologies of non-metallic inclusions; composition of top slag could
change the composition of non-metallic inclusions, and its ability to absorb
and dissolve inclusions could result in less or more clean steel. Generally
among slag-steel-ladle, top slag is the easiest and most powerful parameter
that could be manipulated and optimized.
It could be said that during steelmaking process, slag-steel-ladle make one
system, so in order to study the nature of non-metallic inclusions during
vacuum degassing process these three main factors should always be
considered.
Interactions among slag-steel-ladle at different treatment durations,
temperatures and pressures generate different thermodynamic systems;
thus in order to study non-metallic inclusions both kinetic (time
dependency of reaction rate) and thermodynamic factors should be
considered.
This should be mentioned that during the vacuum degassing processes in
this study, slag-steel-ladle made a dynamic system that was not completely
homogenous and because this system was not truly isolated (even at very
low pressures), it was always altering; these changes probably resulted in
different equilibria at different occasions and at various positions inside the
treatment ladle; thus it could be said that there were always trends that the
system reaches an equilibrium, but because the system parameters were
various and were always changing a homogenously equilibrated system
was not achieved.
In this study it was tried to understand the nature of the metastable that
were achieved during the vacuum degassing; in case it was deeply
understood it would be possible to modify chemical composition, volume
fraction, dispersion, and morphology of non-metallic inclusions that appear
and change during the vacuum degassing process.
During this work it was found that computational thermodynamics is a very
powerful tool that could be very helpful for simulating and optimizing
steelmaking process; however there were some problems and
45
insufficiencies that ought to be solved. It was found that the calculated

results of O, S, and Mg of molten steel were different from the measured
results; however it was known that amount of these elements could always
be changed (because initial input system was not isolated), and there were
even uncertainties about measuring instruments.
Regarding oxygen of molten steel, it was attempted to establish the most
accurate existing models in order to calculate results that were closest to
the measured results. Some regressions and graphs were generated that
could practically be applied by both engineers and operators at melting
plants.
It was seen that chemical compositions, volume fraction, dispersion, and
morphologies of non-metallic inclusions at different positions in the same
steel heat were very different from each other; however it was seen that
non-metallic inclusions were moving toward an equilibrium point, and the
average of their chemical compositions may be possible to be calculated.
It was experienced that some of the challenges regarding SEM analysis of
non-metallic inclusions were finding a standard way to classify, sample, and
prepare steels with the highest possible reliability. Beside, finding results
that could be true representatives of each heat was a challenge too.
Degassing time was found to be a dilemma; long degassing time in
optimized thermodynamic conditions may be positive because it eases the
removal of larger non-metallic inclusions and reduces the TO of final steels,
and it may be negative because it may cause the formation of larger
inclusions, appearance of more calcium aluminates, more erosion and
corrosion of ladle lining, high consumption of resources and lowering
production capacity.
In the ASEA-SKF ladle furnace of this study it was found that depending on
steel grade, 25 to 35 minutes degassing time could be considered as
optimized degassing time. In case of shorter degassing time, reducing H
level of molten steel to the desired levels may become a challenge.
During this study it was shown that regarding O and S contents of molten
steel and degassing time it was possible to change and optimize the vacuum
degassing process.
It could further be added that by increasing alumina capacity of synthetic
top slag or ability of top slag to absorb and dissolve Al rich oxides, it is
possible to add more Al to the molten steel, this Al would generate Al oxides
and reduce oxygen activity of molten steel; then if synthetic top slag is able
46
to absorb and dissolve these non-metallic inclusions (by having high

amount of molten CaO or high CaO activity), it would probably be possible
to reduce the TO of steel products to less than 2ppm.
Although Ca-treatment was not focused in this study, Ca-treatment of
molten steel is known to be a very effective way to generate calcium
aluminates with low melting point; this would facilitate the removal of
unmelted Al and Mg rich non-metallic inclusions, this could also result in
formation of low melting point CaS inclusions.
Based on the sub projects of this work, the author of this report suggests
that during the ladle treatment process in the ASEA-SKF ladle furnace, nonmetallic inclusions might go through several stages (occurrence of some
stages can even overlap):
1. Before start of the degassing and when Al is added to the molten
steel, alumina inclusions form.
2. Some minutes after Al addition (before and during the entire vacuum
degassing), the available Al and alumina react with Mg and MgO, and
form new compounds with chemical compositions close to MgAl2O4
(spinel); Mg could come from different sources such as EAF top slag
left over, synthetic top slag, ladle glaze, and ladle bricks; however
ladle bricks that are made of C bounded MgO are likely to be a very
important source of Mg.
3. After putting the synthetic top slag on the molten steel, Ca that may
enter the ladle either intentionally as the main mineral of the
synthetic top slag (and from Ca-Si wires, in case of calcium
treatment), or unintentionally as a residual component in slag and
alloying additives, react with the available S and O, and depending on
the thermodynamics of the system (pressure of the ladle, S and O
content of the molten steel are very important) CaO or CaS can form.
4. During the degassing process, most of the formed alumina, spinel,
CaO and CaS inclusions enter the optimized top slag that is CaO rich
and cause a reduction followed by an increase of the melting point of
the top slag (at the eutectic point of the CaO-Al2O3 binary system). At
the same time that Ca seek for alumina and spinel inclusions to form
low melting point, thermodynamically stable compounds, available
spinels in favourable thermodynamic conditions (very low S and O
content and low internal pressure of the ladle) can act as nucleation
points for forming complex inclusions composing of calcium
aluminates and spinel inclusions (Ca cover around some of the
47
spinels and form complex Ca-Al-Mg-O inclusions with different ratios

of these elements).
5. Some minutes after the start of the degassing process, and in
optimized conditions, appearance of complex calcium aluminates and
spinels result in the reduction of S and O content of the molten steel
to very low levels; this could even lead to higher ladle erosion (by
absorbing more O from the MgO available in the ladle bricks) and
appearance of more Mg in the slag-steel system.
6. Throughout the entire degassing process, depending on the size of
inclusions, and in case of having optimized steel stirring, most of the
inclusions float toward the surface of the molten steel (it is also
possible that many of them, especially smaller ones cannot reach the
top of the ladle), and if the physicochemical properties of the top slag
are optimized, they could be absorbed by top slag and kept on the
higher parts of the ladle until start of the teeming process.
It is worthy to mention that after the degassing process and during
solidification of steel, several other types of inclusions may form. If the S
content of the steel is high, then MnS inclusions may appear, and in case the
right thermodynamic conditions exist, available active elements such as Mn,
Al, Ti, and Cr may form other compounds, for example nitrides, carbides
and complex inclusions.
During the solidification a part of available sulphur might also cover the
surface areas of some of the oxides (typically forming CaS compounds on
the surface of calcium aluminates).
Mould powder that is applied in the ingots during teeming could also affect
the solidifying steel to some extent; although it is an important factor
affecting some types of inclusions, it was not covered during this PhD work.
48
6. Summary of conclusions
Regarding the calculated results achieved by computational
thermodynamics it was seen that the calculated Al, Mn, and Si contents in
the molten steel and the amounts of Al2O3 and SiO2 in the top slag were in
good agreement with the measurements. The calculated and the measured
O, S and Mg contents in the molten steel, and the S, CaO and MgO contents in
the top slag, were not in good agreement. It was concluded that LiMeS that
is an interface for Thermo-Calc was a useful tool for slag-steel equilibrium
calculations.
Considering theoretical calculations of oxygen in molten steel, both
Wagners and Turkdogan's equations were found to be useful. It was seen
that increasing wt% Al in the molten steel from 0 to 0.05, increasing the
CaO/Al2O3 ratio in the top slag, and reducing the equilibrium temperature
of slag-steel could effectively contribute to the reduction of oxygen activity
of molten steel.
Regarding CaO-Al2O3 ratios in non-metallic inclusions, top slag, and steel
after ladle treatment process, the CaOincl and Al2O3incl in all of the calcium
aluminate inclusions of this study did not have the same ratio; but they
covered a large range. The average CaOincl and Al2O3incl in all samples had
nearly similar compositions that were close to the border of the phase
Ca12Al14O33 in the binary phase diagram of CaO-Al2O3. The CaOslag and
Al2O3slag in all samples had almost similar compositions that were close to
the border of the phase Ca3Al2O6 in the binary phase diagram of CaO-Al2O3.
The results of theoretical calculations were close to the CaOslag and Al2O3slag,
but they did not follow the same maximum and minimum tendencies of the
CaOslag and Al2O3slag.
It was concluded that vacuum degassing process was a dynamic process
and during that spinel and calcium aluminate inclusions were the dominant
types of inclusions. In addition it was seen that during this process
percentage share of the calcium aluminates compared with the spinels, Ca
weight percent content of the oxides, average ECDs of the oxides, and
percentage share of the oxides with bigger ECDs were increasing, and
oxides tended to form more round shapes.
49
It was found that depending on steel grade, 25 to 35 minutes degassing

time could be considered as optimized degassing time in an ASEA-SKF ladle
furnace.
The final results showed that by adding 200 kg fluorite to a top slag of 1200
kg, it was possible to achieve a steel S content of less than 10 ppm and a
(%S)/[%S] ratio of 1570, and at the same time reduce the oxygen activity of
the molten steel and degassing time.
50
7. SUGGESTIONS FOR FUTURE WORKS

Assessment techniques (both destructive and non-destructive) that are
applied for analyzing and classification of non-metallic inclusions should be
more developed and standardized. These techniques should cover micro,
meso and macro inclusions more deeply with higher capability, reliability,
and repeatability.
Databases that are used by computational thermodynamic computer
programs should be further developed and expanded; especially O, S, Ca,
Mg, N that are very crucial elements regarding making cleaner steels;
furthermore more slag properties could be introduced to these computer
programs such as viscosity, foaming index, and sulphur potential.
The possibility of predicting inclusion types depending on the
thermodynamic and kinetic conditions of steelmaking and ladle treatment
process should be further studied and developed.
Behaviour of non-metallic inclusions during vacuum degassing process
should be further observed. By gathering more data from argon protected
liquid steel samples of different steel grades at different thermodynamic
and kinetic conditions it would be possible to optimize steelmaking
processes considering both quality and economical perspectives of the
process.
Aluminium oxide capacity of synthetic top slags should be further studied
and clarified; this would increase the general understanding regarding
possibility of O reduction of molten steel by adding more Al deoxidizer and
would improve the possibility of absorbing generated oxides by an active
slag that would probably result in lower TO in steel products.
Breakability, deformability, melting point, or generally physicochemical
properties of different types of non-metallic inclusions in steel matrix at
different degrees of reduction ratio and their effects on the final products
should be more investigated.
Depending on chemical composition, morphology, volume fraction, and
dispersion of non-metallic inclusions in different steel grades, more data
should be generated and related to the mechanical performance of steel
51
parts. The behaviour of different types of inclusions relative to the

application of steel grades under different loading conditions should be
understood in details. Some types of non-metallic inclusions that are
considered devastating for one application may be very positive for another
application.
It would be useful to study different parts of ingots or rolled bars by SEM in
order to investigate possibility of appearance of some certain types of nonmetallic inclusions in some certain parts of ingots or formed products
(segregation of non-metallic inclusions).
Mg deoxidation of molten steel should be more studied; as it was seen in
this project, spinel inclusions in the respective treatment furnace tended to
have smaller ECDs compared to calcium aluminates, it makes Mg an
interesting element that might be able to replace Ca; however technical and
practical difficulties of using Mg as a deoxidiser should be regarded and
solved.
The possibility of Ca treatment at controlled and optimized different S
contents could also be considered as an interesting approach. During this
study it was observed that CaS inclusions seemed to be as isotropic as
calcium aluminates but with smaller ECDs.
In computational thermodynamic computer programs, although it may be a
challenging task, it should be possible to consider and calculate the amount
of elements that are unintentionally added to the equilibrium system of
slag-steel-ladle after starting the vacuum degassing. Elements such as Mg
that enters to molten steel from ladle bricks, O that may come from added
argon gas, air, and ladle bricks, and N that is added during flushing of
instruments inside the furnace should be possible to be considered,
calculated and added to initial inputted calculation conditions and
parameters. This would give the possibility of calculating actual slag-steelladle system, and not merely slag-steel that are affected by the nature of the
ladle lining and their surrounding environment.
More resistance ladle lining materials should be developed. Specially in so
called clean steels because of the fact that oxygen activity of molten steel is
usually very low, and very active deoxidizers are used, ladle linings should
be much more resistance against both erosion and corrosion. Otherwise the
ladle lining itself could be a source of generating different types of harmful
non-metallic inclusions during steel making process.
52
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Non-metallic inclusions in SEM
62

Slag, Steel, Ladle and Non-Metallic Inclusions Equilibria in An ASEA-SKF Ladle Furnace

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Slag, Steel, Ladle and Non-Metallic Inclusions Equilibria in An ASEA-SKF Ladle Furnace

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Slag, Steel, Ladle and Non-metallic

Inclusions Equilibria in an ASEA-SKF

Slag, Steel, Ladle and Non-metallic Inclusions Equilibria in an ASEA-SKF

Department of Materials Science and Engineering

ISRN KTH/MSE--12/24--SE+ THERM/AVH

Non-metallic inclusions in SEM

1- Slag-Steel Equilibrium Calculations by Computational Thermodynamics:

Authors contributions to each supplement:

Parts of this work have been presented at the following conferences:

2- Top slag optimization in an ASEA-SKF ladle furnace

3- Equilibrium calculations of Slag-Steel in an ASEA-SKF ladle furnace

Harmful effects of non-metallic inclusions are highly dependent on their

Figure 3: General overview of five supplements and their respective objectives.

Figure 4: Logic behind the project and each supplement.

dispersion, composition, and development of non-metallic inclusions in the

2.1. COMPUTATIONAL THERMODYNAMICS

2.2. SULPHUR REMOVAL

2.3. OXYGEN REMOVAL

[Si] + 2[O] SiO2 (s)

G 0 = 581,900 + 221.8T [J/Mol]

2[Al ] + 3[O ] Al2O3 (s)

G 0 = 1,202,000 + 386.3T [J/Mol]

[Ca] + [O] CaO (s)

G 0 = 645,200 + 148.7T [J/Mol]

Each of these elements reduces the oxygen content of molten steel to a

2.4. OXYGEN ACTIVITY CALCULATIONS

2[ Al ] + 3[O ] Al2O3 (s)

G 0 = 1,202,000 + 386.3T j/mol

log f Al = eAlj [wt % j]

Turkdogan's equation [97]: Equation (14) is a simplified way to present

2.5. NON-METALLIC INCLUSIONS

Figure 5: Chemical compositions (normalized to ACM) and typical ECDs (m) of

Figs. 6 and 7 show two different examples of SEM-EDS mapping analysis of

Figure 6: SEM-EDS mapping analysis of two calcium aluminates.

Figure 7: SEM-EDS mapping analysis of two spinels.

It should be mentioned that at the beginning of the vacuum degassing

2.6. REMOVAL OF NON-METALLIC INCLUSIONS

S: Rate of inclusion removal due to flotation

Sb: Rate of non-metallic inclusions entrapment

3- Ca-treatment is another effective way that could facilitate the removal

Figure 8: Schematic of the steel melting plant of Ovako Hofors AB.

3.2. SAMPLE ANALYZING METHODS

4.1. RESULTS OF SUPPLEMENT 1

4.2. RESULTS OF SUPPLEMENT 2

Figure 12: O versus wt% Al at different temperatures and CaO/Al2O3 ratio.

O = 19.9 + 0.0158Temp 4.42[Al] 0.0491(CaO)

Both Wagner and Turkdogan's equations were useful for calculating

Most of the oxygen activity results that were calculated theoretically

If the measured oxygen activities of the molten steel by means of

Positive effect of Al addition to molten steel in order to reduce oxygen

Temperature of molten steel was an important factor that affected

Higher ratio of CaO/Al2O3 could result in less oxygen activities of

Two regressions were generated that are supposed to be useful to

4.3. RESULTS OF SUPPLEMENT 3

The CaOslag and Al2O3slag in all samples had almost similar

4.4. RESULTS OF SUPPLEMENT 4

Figure 17: Changes of the amounts of components in samples and temperature

Figure 18: Oxides observed in five samples of this study.

Results achieved form this study could be summarized as follow:

spinels and calcium aluminates were the dominant types of

several factors such as temperature and top slag-steel compositions

percentage share of calcium aluminates, compared to spinels were

Ca weight percent content of oxides was increasing.