Control of Ca addition for improved cleanness

of low C, Al killed steel

S. Abdelaziz1, G. Megahed2, I. El-Mahallawi*3 and H. Ahmed4
In this work, heat trials (14 heats made on two sequences) were conducted to identify the
minimum Ca addition possible for preventing submerged entry nozzle clogging and for improving
the steel Cleanness. These trials were conducted on two sequences, the first one aimed at
reaching the minimum Ca addition practically possible and the second aimed at stabilising this
addition level. Evaluation of the results was carried out using metallographic microscope
observation and SEM/EDX analysis. It was found that submerged entry nozzle clogging was
successfully prevented by decreasing the amount of Ca addition from 0?095 to 0?06 kg Ca/ton
steel. Moreover, it was possible to identify the effect of such addition level on converting alumina
inclusions to globular Ca–aluminate and reducing the CaS inclusion formation range from 4–41 to
0?05–7?61%.
Keywords: Clean steel, Calcium treatment, Non-metallic inclusions in steel

Introduction The amount of Ca reacting with aluminium oxide

With growing demands for quality steel, cleanness of
steel becomes more and more important. Steel cleanness
is controlled by a wide range of operating practices
throughout the steelmaking processes. These include the
time and location of deoxidant and alloy additions,
extent and sequence of secondary metallurgy treatments,
such as stirring and transfer operations, shrouding
systems, tundish geometry, absorption capacity of the
various metallurgical fluxes, and casting practices.
In low carbon Al killed steel (LCAK) production, Al
is added to deoxidise the steel. Deoxidation products
(non-metallic inclusions) have a density lower than that
of steel; thus, these inclusions tend to rise out of the
liquid steel to the slag. However, many of these
inclusions particles are small to rise rapidly and tend
to remain in the steel. Stirring with argon bubbling
promotes agglomeration of the inclusions to larger
clusters which can rise faster. Nevertheless, some
alumina inevitably remains in the liquid steel even after
argon stirring.1–5
To prevent build-up of these inclusions in the
submerged entry nozzle (SEN), Ca is injected into the
liquid steel. Ca treatment has been introduced to control
the properties of inclusions. Ca is added to liquid steel
by wire injection of pure Ca or ferroCa or Ca silicon or
Mg–Ca alloys. Ca reacts with aluminium oxide particles,
which results in the transformation of solid aluminium
oxide inclusions into liquid Ca aluminate.6,7
1
2
Cairo University, Cairo, Egypt
Tabbin Institute for Metallurgical Studies (TIMS), Cairo, Egypt
3
British University in Egypt (BUE), El Sherouk City, Cairo, Egypt
4
Department of Metallurgy, Faculty of Engineering, Cairo University, Cairo,
Egypt
*Corresponding author, email ielmahallawi@Bue.edu.eg
must be controlled; otherwise, solid Ca aluminates are
formed. This is less straightforward than it seems: Ca
has a very low solubility in liquid steel and therefore, the
efficiency of Ca additions is low. Furthermore, Ca must
react homogeneously with all aluminium oxide in the
steel melt; otherwise, Ca poor or Ca rich aluminates are
formed. Castability decreases by the presence of the high
melting Ca aluminates inclusions, which may be even
worse than the aluminium oxide. The cost, low efficiency
and necessary high process control make Ca treatments
difficult.5–9
This study aims at evaluating the effect of production
parameters on non-metallic inclusions level at the steel
melting shop in Ezz Flat Steel (EFS) plant. The impacts
of aluminium addition, stirring and slag composition on
inclusion removal and modification were investigated.
The study also aims at investigating the influence of the
amount of Ca, which is used in Ca treatment process in
secondary metallurgy process, on the quality of pro-
duced steel and determination of the optimum amount
of Ca required for inclusions modification which has an
important role in improvement of steel cleanness. In this
work, trials were made on two sequences (14 heats) to
reach the minimum Ca addition possible for preventing
SEN clogging and for improving the steel cleanness: the
first one for reaching the minimum Ca addition
(practically possible) and the second for stabilising this
addition level.
Experimental
Industrial process description
The secondary metallurgy at EFS starts with tapping
185 tones of steel from the electric arc furnace to the
ladle, at 1650uC and 700–1000 ppm oxygen. During
tapping slag forming material, alloying elements and

ß 2009 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 1 July 2007; accepted 17 October 2007
432 DOI 10.1179/174328109X401578 Ironmaking and Steelmaking 2009 VOL 36 NO 6
 Abdelaziz et al. Ca addition for improved cleanness of LCAK steel

deoxidant can be added. After tapping, the ladle is Table 2 LRF slag analysis for eight heats of experimental
transferred to the ladle furnace refining unit (LRF) to programme
conduct the steel refining starting by complete reduction Heat no. Step CaO Al2O3 MgO SiO2 Fe2O3 Fe2O3 MnO
of the slag by Al grains and then treating the steel bath
by Al wire. The final slag composition after complete 1.1 Arr. 54 25.6 8.04 3 7.23 0.585
deoxidation is such that a low melting point liquid slag is Dep. 57.1 33.2 6.59 1.08 0.84 0.074
obtained. After slag building and raising the tempera- 1.3 Arr. 51.9 31.8 6.72 2.61 6.03 0.56
ture of the steel to y1620uC, desulphurisation process is Dep. 54.8 34.3 6.13 1.22 0.74 0.022
1.6 Arr. 51.1 28.7 6.64 2.33 7.39 0.37
started by applying the intensive stirring of argon for 8– Dep. 55.5 35 6.14 0.65 0.87 0.038
10 min to reduce the sulphur content to less than 5 ppm. 1.7 Arr. 50.4 30 7.34 2.77 4.26 0.49
After the required chemical analysis and temperature are Dep. 54.7 31.8 6.7 1.02 0.82 0.05
obtained, the steel is stirred by soft argon bubbling for 2.1 Arr. 49.1 23.6 5.81 3.01 7.72 0.6
y15 min to float the non-metallic inclusions to the slag. Dep. 56.3 33.6 6.27 1.15 0.92 0.06
Finally, Ca treatment is carried out to modify the 2.2 Arr. 51.9 31.8 6.72 2.61 6.03 0.56
Dep. 56 33.6 6.81 0.66 0.9 0.037
inclusions shape and content in the steel bath by Ca 2.3 Arr. 49.8 32.5 6.49 2.63 7.65 0.44
powder cored wired injection followed by soft argon Dep. 57.4 33.2 6.43 1.22 0.53 0.04
bubbling for y10 min to complete the inclusions 2.4 Arr. 48.9 26.2 5.86 4.21 11.2 0.79
modification and to float the inclusions to the slag. Dep. 57.7 31.1 6.09 1.89 0.9 0.06
After Ca treatment is finished, the ladle is transferred to
the thin slab caster to start casting. The normal
80 m min21 using a refractory lance. The depth of
productions at that stage before conducting the research
injection was 2 m under the steel surface. The Ca wire
adopted using Ca addition ranges between 0?092 and
was injected through a refractory lance under argon
0?108 kg/ton steel.
flowrate of 35 nL min21 and pressure of 5 bar. The wire
Minimising amount of Ca addition lance method ensures that the Ca wire travels in a
In this work, trials were made on two sequences (14 straight downward line after entering the bath. The Ca
heats) to reach the minimum Ca addition possible for recovery for additions with the wire lance process is
preventing SEN clogging. These trials were conducted y30%.
on two sequences, the first one for reaching the
minimum Ca addition practically possible and the Material description
second for stabilising this addition level. In the first Steel samples
sequence, minimisation trials were conducted gradually The steel chemical analysis of all the heats was checked
on six heats starting from the second heat to reduce Ca by standard steel sampling using dual samples (lollipops)
addition from 0?076 to 0?055 kg/ton steel in the last heat to measure the chemical composition of the steel using
in this sequence, after which production problems an optical emission spectrometer. The samples were
started. The minimisation was conducted gradually to taken after tapping, before and after desulphurisation,
avoid sudden problems causing line stoppage. In the before and after Ca treatment, at the end of the ladle
second sequence, starting from the second heat, the Ca metallurgy and from tundish during casting at 50% steel
addition was fixed at an amount of Ca (0?06 kg/ton remaining in the ladle. Table 1 shows the steel final
steel) for the six heats in this sequence, as 0?06 kg/ton chemical analysis of ladle samples for the 14 produced
steel was the limit point after which production heats.
problems started to appear. During casting of both
sequences, some important process parameters (shroud Slag samples
and stopper rod position) were monitored. Stopper rod Slag composition of the heats of the two sequences was
positions indicate success of casting process in terms of checked by taking slag samples at the start of treatment
no clogging occurring in the SEN. process and slag samples at the end of the ladle
In all heats, the Ca was added by wire lance method. treatment, and the samples were ground into powder,
An 8 mm diameter (steel clad wire containing 0?06 kg cast into glass discs and analysed using an XRF system
pure Ca/m) was injected on the steel bath at a rate of (model: Bruker AXS S4). Table 2 shows the obtained

Table 1 Steel final chemical analysis of ladle samples

C Si Mn P S Ca Al

First sequence 1.1 0.029 0.015 0.16 0.004 0.0013 0.0031 0.028
1.2 0.038 0.017 0.17 0.004 0.0019 0.0028 0.034
1.3 0.031 0.018 0.16 0.004 0.0027 0.0026 0.033
1.4 0.044 0.016 0.17 0.002 0.001 0.0027 0.031
1.5 0.035 0.035 0.17 0.005 0.001 0.0024 0.032
1.6 0.033 0.021 0.18 0.004 0.0018 0.0023 0.030
1.7 0.035 0.020 0.19 0.004 0.001 0.0018 0.032
Second sequence 2.1 0.037 0.018 0.18 0.005 0.0021 0.0032 0.032
2.2 0.036 0.011 0.17 0.002 0.0062 0.0023 0.035
2.3 0.037 0.016 0.19 0.004 0.0017 0.0023 0.031
2.4 0.034 0.010 0.17 0.004 0.004 0.0025 0.032
2.5 0.035 0.018 0.18 0.005 0.0041 0.0022 0.037
2.6 0.036 0.014 0.17 0.003 0.0043 0.0024 0.036
2.7 0.029 0.027 0.18 0.005 0.0019 0.0021 0.030

Ironmaking and Steelmaking 2009 VOL 36 NO 6 433

Abdelaziz et al. Ca addition for improved cleanness of LCAK steel
slag analysis for the eight heats included in the experi-
mental programme. The increase or decrease in oxides in
slag will be used in this analysis as a guide to reactions
taking place between the slag and the metal.
Non-metallic inclusions evaluation
The number, size, shape and composition of non-
metallic inclusions in LCAK steel samples were per-
formed using metallographic microscope observation,
image analyser and scanning electron microscope with
energy dispersive X-ray (EDX).
Sample preparation
For cleanness investigations, the following metallo-
graphic preparation technique has been adopted. First,
the samples were ground manually with SiC paper
(granulation 180–1200) and then polished semiautoma-
tically using ethanol as lubricant. Special polishing
cloths, 3 mm and afterwards 1 mm diamond suspension,
were used for optimal sample preparation. It is
absolutely essential to check the result of the prepara-
tions under an optical microscope. This is necessary to
ensure only a few abrasive grains are detectable in the
surface and to check that the inclusions have not been
broken loose during metallographic preparation.
To assure the direct correlation between the studied
parameters and the NMI evaluation, it was necessary to
standardise some other production parameters. Thus, all
the plant trials were carried out under the following
conditions in the steel plant assuring that a clean steel
practice was followed at the ladle furnace (ensuring that
the total oxygen content is similar for each ladle). The
main elements of this practice were:
(i) aluminium addition was made during tapping to
deoxidise most of the oxygen content from
molten steel early before the start of refining
process
(ii) argon stirring was made during steel tapping to
the ladle, through a porous plug to enhance non
metallic inclusions collisions and flotation
(iii) avoiding electric arc furnace slag carryover
during tapping as much as possible to prevent
steel reoxidation during refining process
(iv) completing reduction of ladle slag at the start of
treatment to prevent steel reoxidation
(v) final aluminium addition was made at least 15–
20 min before Ca treatment, to maximise inclu-
sions flotation
(vi) soft argon purging of the steel (giving an ‘eye’ in
the slag surface of 100 mm diameter maximum)
was performed directly before Ca was added to
the steel
(vii) soft argon purging of the steel was performed for
10 min after Ca addition to ensure complete
modification of inclusion
(viii) melt contact with air was avoided/minimised
after Ca additions, since new unmodified alu-
mina would form by reoxidation
(ix) the FeO content of the slag was controlled to
avoid reoxidation of aluminium by the slag
(x) controlling slag composition of the heat to verify
the conditions of alumina dissolution during
flotation by argon.
434 Ironmaking and Steelmaking 2009 VOL 36 NO
Results and discussion
The solubility of Ca in iron at 1607uC at 1 atm pressure
is 189 ppm Ca,10 C, Si, Ni and Al increase the Ca
solubility markedly. However, the addition of Ca to steel
initially results in a more or less pronounced conversion
of the alumina into Ca aluminates until the formation of
Ca sulphides starts as the addition of Ca continues. Ca
sulphides are solids at steelmaking temperatures and
may lead to nozzle clogging similar to that caused by
alumina. The range in which all the oxides have been
liquefied without formation of solid sulphides is the
target of Ca treatment. Its precise location depends on
the steel’s sulphur and total oxygen contents.7,11
Effect of Ca addition on casting process
Sufficient data were collected from the normal produc-
tion stages to monitor the relation between Ca addition
and Ca ppm content in steel, which showed that Ca
content in steel remains within the range 18–28 ppm in
tundish, irrelevant of the amount of added Ca which
ranged from 0?092 to 0?108 kg/ton steel. These data
agree with reported data informing12 that injecting more
Ca leads to low Ca retention efficiency. Based on
reported data12 that when total Ca/total oxygen ratio
reaches 0?6, conditions become favourable for obtaining
clean steel, and since, the total oxygen content in Al
killed steel at final treatment is usually within the range
of 30–40 ppm, by a simple calculation and assuming Ca
retention values of 30%,12 which means that Ca within
the range 0?05–0?06 kg/ton is sufficient for treatment of
steel. Thus, it was decided to study the effect of reducing
Ca addition gradually from 0?095 down to 0?055 kg Ca/
ton steel in the first seven heats named the first sequence.
During this first sequence, the castability was deter-
mined as a function of Ca addition and it was noticed
that production problems occurred (caused by clogging
of submerged entry nozzle) when Ca addition reached
0?055 kg Ca/ton steel. Therefore, it was decided to work
during the next seven heats named the second sequence
with 0?06 kg Ca/ton steel. At this level of Ca addition,
the casting process continued without any problems
which cause line stoppage and production delay.
During casting of both sequences, stopper rod
position was monitored. Stopper rod level indicates
success of casting process in terms of no clogging
occurring in the submerged entry nozzle. Stopper rod
was stable during casting of all heats except for heat 1?7
which contains 0?055 kg Ca/ton steel.
Effect of Ca addition on Ca yield in ladle and
tundish
The effect of Ca addition on Ca yield in ladle and
tundish is present in Table 3. Figure 1 shows the
relationship between Ca addition and Ca yield in ladle
and tundish. This figure shows that Ca yield in ladle and
tundish increases by increasing the Ca addition. It is to
be expected that the Ca retention in tundish will be
lower than the Ca content in ladle because of flotation of
Ca containing inclusions out of the steel bath in the time
before casting. Floatation of inclusion explains that the
Ca content of steel drops as it moves from the ladle to
the tundish as shown in Fig. 1. Data reported from
numerous plant trials have shown that the Ca retention
efficiency drops with increasing quantity of Ca
injected,12 and that the amount of Ca injected has to
6
 Abdelaziz et al. Ca addition for improved cleanness of LCAK steel

Ca(l)~Ca(g) (1)

Ca(g)~½Ca
(2)

½Ca
z½O
~CaO (3)

½Ca
z½S
~CaS (4)

½Ca
z(xz1=3)Al2 O3 ~CaO:xAl2 O3 z2=3½Al
(5)

1 Relationship between Ca addition and Ca yield in ladle
and tundish
be adjusted with the total oxygen content of the steel. A
criterion derived12 for the tundish composition ranges
for Al killed steels to achieve acceptable sulphide shape
control has shown that for total oxygen (as aluminate
inclusions) of 25 ppm, Ca needed is 20–30 ppm, and for
total oxygen (as aluminate inclusions) of 12 ppm, Ca
needed is 15–20 ppm.
The material balance for Ca consumption can be
expressed as follows12
Wi ~Wb zWo zWo0 zWs zWv
where Wi is the amount of Ca injected, Wb is the amount
of Ca dissolved in the bath, Wo is the amount of Ca
present in aluminates and sulphides, W9o is the amount
of Ca reacted with alumina and subsequently floated
out, Ws is the amount of Ca reacted with the slag and
Wv is the amount of Ca escaped via the vapour phase
and subsequently burnt at the bath surface.
When the operation practices in the ladle and tundish
are stable, the values of Wo, W9o, Ws and Wv do not
change while Wb increases with increasing Ca addition
which explains the increase in Ca yield in the ladle and
tundish by increasing the Ca addition Wi. Transferring
steel from ladle to tundish leads to drop in the
temperature and has a strong effect on the Ca yield of
tundish steel which decreases as shown in Fig. 1. Upon
adding Ca in any form to Al killed steel, containing
alumina inclusions and sulphur, the following series of
reactions are expected to occur12,13
(CaO)z2=3½Al
z½S
~(CaS)z1=3(Al2 O3 ) (6)
The following equation has been presented to
combine the simultaneous occurrence of equations (5)
and (6)
3{2y 2
(CaO)x (Al2 O3 )1{x z AlzS~
3x{3y 3
3{2x
(CaO)y (Al2 O3 )1{y zCaS (7)
3x{3y
where the symbols within square brackets refer to
species dissolved in steel, and those within parentheses
are dissolved in the aluminate phase. According to
reported observations by a number of investigators,14
the extent to which equation (3) occurs is negligible, and
probably equation (4) will start taking place simulta-
neously, whereas for steels with sufficiently low S
content, equaton (5) will take place first, followed by
equation (6). The issue here is the amount of Ca
available to enter into equation (5) after equation (4)
has completed, and which depends on the sulphur
content. Simple calculations based on equations (4) and
(6) would reveal the critical sulphur and aluminium
contents necessary for the modification of the solid Ca
aluminates into liquid Ca aluminates. Injecting more Ca
than can react with the available inclusions leads to a
low Ca retention efficiency.
The fact that there is a linear increase in Ca% in ladle
with increasing injected Ca indicates that the thermo-
dynamic conditions follow Henry’s law between 0?06
and 0?095%Ca additions, after which the thermody-
namic conditions deviate from Henry’s behaviour and
retention of Ca drops. The conditions seem to be
different in the tundish. However, the drop in Ca% from
ladle to tundish indicates that conditions become

Table 3 Ladle and tundish analyses for Ca and N

Heat no. Ca added, kg/ton steel Ca in LRF, ppm Ca in TD, ppm Ca drop, ppm

First sequence 1.1 0.095 31.5 24 7

1.2 0.076 28 20 8
1.3 0.070 26.5 20 6
1.4 0.070 27 21 6
1.5 0.060 24 19 5
1.6 0.060 23.13 18 5
1.7 0.055 18 14 4
Second sequence 2.1 0.095 32 22 10
2.2 0.060 23 18 5
2.3 0.060 23 17 6
2.4 0.060 25 21 4
2.5 0.060 22 18 4
2.6 0.060 24 20 4
2.7 0.060 21 18 3

Ironmaking and Steelmaking 2009 VOL 36 NO 6 435

Abdelaziz et al. Ca addition for improved cleanness of LCAK steel

favourable (e.g. temperature drop) for some amount of

the Ca to enter into other reactions forming sulphides.

Effect of Ca addition on refractories

The injected Ca not only modifies the inclusions as
described before but also can react with the refractory in
ladle and tundish. Corrosive attack of refractories is
considered as the main source of large inclusion in the
steel. Thus, corrosive attack on ladle lining refractories
and tundish refractories must be considered in Ca
treatment process.15 To study the effect of Ca content
on refractories, the attack of stopper rod refractories
during steel casting is calculated as shown in Table 4.
Decreasing Ca addition from 0?095 to 0?06 kg/ton steel
reduces the attack of stopper rod refractories by y25%.
This indicates that reduction of Ca addition reduces
ladle lining refractories and tundish refractories (tundish
lining, stopper rod, ladle nozzle plate) attack. As the
corrosive attack in refractories is reduced, the likeliness 2 Deoxidation with Al in equilibrium with Al2O3 or molten
of improvement in cleanness of the steel is expected, as Ca–aluminates6
there is a less chance for macrometallic inclusions to be
around. best results were obtained when aluminium was added in
one batch for steel deoxidation during tapping with
Steel cleanness evaluation vigorous argon stirring. In this case, clusters were
Analysis of ladle steel formed, which were largely removed within few minutes.
Ladle refining stage is particularly important to improve The oxygen sensor reading for soluble oxygen content in
steel cleanness which can be achieved by controlling equilibrium with Al in the steel after tapping and at the
total oxygen content, FeO and MnO in the slag, ladle end of ladle treatment is shown in Table 5.
stirring and inclusion modification treatment. To This table shows that when the aluminium content
evaluate the effect of Ca reduction on steel cleanness ranges between 0?028 and 0?095%, soluble oxygen
in ladle, the effect of steel deoxidation, slag composition ranged between 2 and 4 ppm for all cases, which is
and argon stirring on steel cleanness before Ca addition within the normal range reported for Al killed steel.12
will be discussed. However, the oxygen sensor readings v. aluminium
analysis of steel samples collected from ladle after
Steel deoxidation tapping and at the end of steel refining process (Fig. 2)
Half ball aluminium was added to the steel bath in one plotted on line diagrams,6 showing equilibrium between
batch during tapping and trimming by Al wire at the both dissolved oxygen and aluminium in steel and pure
ladle furnace station. Previous studies4 proved that the Al2O3 and molten CaO.Al2O3, with CaO/Al2O351 : 1,

Table 4 Effect of Ca addition on stopper rod attack

First heat 2.1 Last three heats in second sequence

Ca addition, kg/ton steel 0.095 0.06

Average casting temperature, uC 1556 1555
Casting time, h 1 3
Attack, mm 3.5 7.8
Attack, mm h21 3.5 2.6

Table 5 Oxygen sensor reading for soluble oxygen content in steel

Free oxygen measurements, ppm Al, %

Heat no. Before tap LRF start LRF end LRF start LRF end

1.1 923 3 3 0.030 0.028

1.2 666 2 3 0.064 0.034
1.3 711 4 4 0.067 0.033
1.4 634 3 2 0.075 0.031
1.5 891 4 4 0.044 0.032
1.6 701 4 3 0.075 0.03
1.7 670 2 4 0.095 0.032
2.1 745 2 4 0.088 0.032
2.2 783 3 3 0.080 0.035
2.3 803 2 4 0.054 0.031
2.4 962 3 3 0.072 0.032
2.5 721 2 3 0.066 0.037
2.6 735 3 – 0.065 0.037
2.7 956 – 3 0.048 0.030

436 Ironmaking and Steelmaking 2009 VOL 36 NO 6


lies within the range of forming solid and liquefied non-
metallic inclusions. In general, the activity of alumina in
Ca–aluminate inclusions is less than unity. Thus the
activity of oxygen in steel in equilibrium with a Ca–
aluminate is less than that in a steel in equilibrium with
alumina only. Therefore, it is necessary to remove Al2O3
inclusions from the steel bath to reduce the total oxygen
total of the steel bath. This total oxygen Ototal is the sum
of free soluble oxygen and insoluble oxygen as inclusion
(OsolzOins).
The results shown from (Fig. 2) suggests that the
degree of inclusion modification determined by measur-
ing the activity of oxygen in the steel by oxygen sensor,
as has been suggested by others,12 may indicate the
extent of deoxidation; however, since free oxygen does
not vary much, the total oxygen is a reasonable indirect
measure of the total amount of oxide inclusions in steel.
The scatter in the results obtained in this work is
probably due to the varied CaO content in the CaO–
Al2O3 inclusions.
The following equation has been presented to show
the equilibrium relation between aluminium and oxygen
(for low Al%), during oxidation: logK5log([%Al]2[O]3)5
62780/T (K)z20?54.3 According to this equation for
%[Al] of 0?03–0?09%, the free oxygen is 3–5 ppm, which
agrees with the findings in this study.
Slag composition
Slag properties such as CaO/%l2O3 ratio, slag basicity
and oxygen activity affect the cleanness of steel.
Previous studies16 concluded that control of the CaO/
Al2O3 ratio in the range 1?7–1?8 is the most efficient
method in removing inclusions from the steel bath.
Table 2 shows the slag analysis of slag samples collected
from eight heats of experimental program after tapping
(arrival) and at the end of ladle treatment (departure).
This analysis shows that the CaO/Al2O3 ratios at the end
of treatment range between 1?6 and 1?9.
An important source of reoxidation is the slag
carryover from the steelmaking furnace during tapping
to the ladle which contains a high content of MnO and
FeO. These liquid oxides react with the dissolved
aluminium to generate solid alumina inclusions in the
liquid steel, according to the following reactions16
3(MnO)z2½Al
~(Al2 O3 )Inc z3½Mn
(8)
3(FeO)z2½Al
~(Al2 O3 )Inc z3½Fe
(9)
Larger FeOzMnO content in the ladle slag corresponds
to higher total oxygen. For this reason, the slag
carryover from the steelmaking furnace during tapping
must be controlled. From equations (8) and (9), when
the contents of FeO and MnO in slag are high, non-
metallic inclusions are produced; therefore, it is essential
to reduce the FeO and MnO contents in the slag to
improve the steel cleanness. Table 2 shows that FeO and
MnO slag contents at the start of treatment were high
and fluctuate between 4?75 and 11?99%, depending on
the amount of slag carry over during steel tapping from
EAF. These content ratios were reduced to 0?57–1?17%
after slag treatment by lime, Ca–aluminate, bauxite and
Al grains.
Argon stirring
In order to homogenise the steel bath and to enhance
collisions between inclusions, the steel is stirred by inert
Abdelaziz et al. Ca addition for improved cleanness of LCAK steel
gas bubbling. The non-wetting properties of the inclu-
sions help them to separate from the liquid steel and
attach to the gas bubbles, the refractory walls and the
slag/steel interface. Lower total oxygen contents can be
achieved by a more efficient stirring procedure and by
enhancement of cluster formation during deoxidation of
the steel bath. Also, oxygen content before deoxidation
do not affect the cleanness if the steel bath stirred for
y15 min after steel deoxidation by aluminum.4,5
The effect of argon stirring on cleanness of steel is
presented in Figs. 3 and 4. Representative optical
micrographs17 of polished samples were studied by
image analysis method. These samples were taken from
the ladle during preparation of heat 2?2 at the start of
refining process, and before and after (10 and 15 min)
soft bubbling (before Ca addition). Image analysis (IA)
technique is an established3 method for evaluating steel
cleanness, by distinguishing dark and light regions based
on a greyscale cutoff, though not accurate as it is subject
to errors by mistaking scratches and pits, and it was just
used here for comparison reasons. The black spots in
Fig. 3 were checked by refocusing to be sure that they
represent non-metallic inclusions. In spite of limited
evidence, Fig. 3 illustrates that soft bubbling before Ca
treatment enhances inclusions removal from the steel
bath in Al killed steels. After y15 min, soft bubbling–
stirring causes a decrease in count of non-metallic
inclusions. Figure 4 shows the distribution of non-
metallic inclusions size count by image analysis system.
As shown in this figure, as the stirring time increases, the
removal of the large size inclusions from the steel bath
increases, consequently improving steel Cleanness. After
y10 min, soft bubbling–stirring causes a drop in non-
metallic inclusions count, and after 15 min, steel
cleanness is further improved. Since Ca–aluminates
separate from the steel less easily than aluminium oxide
particles, Ca addition can best be delayed until the rate
of Al2O3 removal has become insignificant.
EDX analysis of non-metallic inclusions
Table 6 shows EDX analysis of non-metallic inclusions
of steel samples. LRF samples taken after 3 min from
the end of Ca addition from heats 1?1 and 2?3 which
have been treated with 0?095 and 0?06 kg Ca/ton steel
respectively. Tundish samples taken during casting of
heats 1?1, 1?7, 2?1, 2?2, and 2?3 at 50% steel remain in the
ladle. The analysis was carried out using EDX analyser
mounted on scanning electron microscope of type Jeol
5410. Freshly prepared metallographic samples were
used in such analysis. Elemental analysis of Mg, Al, Si,
S, Ca and Fe were determined. The EDX program uses
the elemental analysis data to calculate the correspond-
ing oxides MgO, Al2O3, SiO2, SO3, CaO and Fe2O3.
However, it should be noticed that EDX analysis is not
accurate for analysing particles ,5 mm and the matrix
effect is likely to interfere. This means that the analysis
of Fe should be considered with care.
It was assumed that all the sulphurs are present as a
CaS and all the irons are present as FeO.8,12,18 The data
obtained from EDX analysis for Fe and S were
converted to FeO and CaS, and accordingly, the
remaining Ca was converted to CaO. The oxygen in
non-metallic inclusions was calculated from the oxygen
present in all oxides. Thus, the composition of each
inclusion was calculated by assuming it to be a mixture
Ironmaking and Steelmaking 2009 VOL 36 NO 6 437
Abdelaziz et al. Ca addition for improved cleanness of LCAK steel
3 Non-metallic inclusions after stirring in ladle furnace (heat 2?2)
of MgO, Al2O3, SiO2, CaO, CaS and FeO as shown in
Table 7.
Representative shapes of different types of non-
metallic inclusion are shown as SEM images in Fig. 5.
It illustrates that the inclusions have a large globular
shape, typical for Ca–aluminate inclusions. The fact that
all detected inclusions possessed that shape indicates
4 Distribution of inclusions found in LRF sample (heat 2?2)
438 Ironmaking and Steelmaking 2009 VOL 36 NO
that even after reducing the amount of Ca (0?06 kg/ton
steel), this amount of Ca was enough for modifying the
alumina inclusions.
Generally,8,18 for pure CaO–Al2O3 system, the addi-
tion of Ca will initially transform the alumina to solid
phase CaO.6Al2O3 (CA6), then to solid phase
CaO.2Al2O3 (CA2), next to liquid phase CaO.Al2O3
6
 Abdelaziz et al. Ca addition for improved cleanness of LCAK steel

Table 6 Inclusions composition after calculations: A, B and C do not represent same type from one heat to another but
just indicate different type for each specific heat

Ca,
Type %MgO %Al2O3 %SiO2 %FeO %CaS %CaO ppm Ocombined Ca/Ototal Type Size, mm

1.1 LRF A* 6.45 43.9 3.81 4.26 1.42 38.5 28.3 36.2 0.78 Fully modified C12A7 12
B 4.3 42.2 10.4 1.77 0.25 40.7 29.2 36.4 0.80 Fully modified C12A7 70
C 8.6 33.9 1.57 23.2 1.82 26.7 20.1 32.6 0.62 Partially modified 30
2.3 LRF A 5.5 45.4 1.29 2.79 0.95 42.9 31.2 36.8 0.85 Fully modified C12A7 40
B 27.6 39.2 0.78 10.0 1.33 18.6 14.0 37.2 0.38 Partially modified 7
C 71.7 4.57 0.22 18.0 0.47 2.60 2.12 35.4 0.06 Spinel 3
1.1Td A 0.83 17.6 1.26 – 41.02 1.70 24 9.42 2.55 Partially modified CA6.CAS 5
B 1.11 49.9 1.8 – 6.48 35 28.6 34.4 0.83 Partially modified C12A7.CS 5
1.7 Td A 0.86 52.6 – – 7.61 17.98 17.1 28.4 0.50 Partially modified CA2.CaS 3
B 6.75 64.3 – – 4.52 17.86 15.3 38.1 0.40 Partially modified CA2.CaS 3
C 14.6 70.4 – – 0.05 12.16 8.71 42.4 0.21 Partially modified CA2 3
2.1Td A – 47.7 1.31 9.84 4.21 31.97 25.2 34.1 0.74 Partially modified CA.CaS 7
B – 24.5 0.99 – 34.83 8.75 25.6 14.3 1.79 Partially modified CA2.CaS 7
2.2 Td A 8.35 66.56 2.15 – 1.71 19.70 15.0 40.8 0.37 Partially modified CA2.CaS 5
B 1.28 67.2 3.04 – 4.50 19.94 16.8 38.6 0.43 Partially modified CA2.CaS 2.5
C 3.89 59.5 2.82 – 3.44 27.32 21.4 38.1 0.56 Partially modified CA.CaS 3
D 3.8 61.3 1.79 – 1.26 30.66 22.6 39.6 0.57 Partially modified CA.CaS 9
2.3 Td A 0.83 17.6 1.26 – 2.61 26.45 20.4 38.6 0.53 Partially modified CA2.CaS 4
B 1.11 49.9 1.8 – 3.13 26.84 20.9 38.5 0.54 Partially modified CA.CaS 5
C 0.86 52.6 – – 0.77 26.96 19.7 40.2 0.49 Partially modified CA 4
*A, B and C just indicate different types of non-metallic inclusions for each heat.

(CA) and finally, to liquid phase 12CaO.7Al2O3
(C12A7). However, the amount of the extent to which
non-metallic formation takes place depends on the total
amount of Ca and sulphur. The addition of Ca initially
results in conversion into Ca aluminates (owing to the
higher affinity of Ca to oxygen than for sulphur), until
the formation of Ca sulphides starts as the Ca addition
continues. The conversion of alumina into Ca alumi-
nates occurs until all the inclusions in the steel are in the
liquid form. If the addition of Ca proceeds further, the
formation of solid Ca sulphides occurs. However, it
seems that the formation of CaS occurs simultaneously,
as analysis of the non-metallic inclusions in this work
has shown that Ca sulphide aluminates have formed
rather than Ca aluminates.
The shapes of the different types of non-metallic
inclusions classified in this work for the tested condi-
tions, given in Table 6 and shown in Fig. 5, are generally
identified in terms of their CaO and CaS contents and
their sizes, an example for inclusions in heat 1?1 being as
follows
(i) the first type A: Ca sulphide aluminate inclusions
of composition CA6.CaS, containing 1?7%CaO
and 41?02%CaS
(ii) the second type B: Ca–aluminate of composition
C12A7CaS fully modified liquid inclusions con-
taining 35%CaO and 6?48%CaS.
A similar analysis for all heats is illustrated in Table 6
from which it is seen that the non-metallic inclusions
found prove the benefit of reducing the amount of Ca
from one heat to another.
Formation of CaS inclusions
Figures 6 and 7 summarise the distribution of CaS
content of the modified inclusions obtained by EDX
analysis for LRF and tundish samples respectively.
Figure 6 shows that CaS content of modified inclusions
in LRF samples was low, ranging between 0?25 and
1?82% at 1590uC. Figure 7 shows that CaS content of
the modified inclusions in tundish samples increased to
0?05–7?61% in samples of heats treated by 0?06 kg Ca/
ton steel and to 4?21–41?02% in samples of heats treated
by 0?095 kg Ca/ton steel.
The higher contents of CaS inclusions found in
samples of heats 1?1 and 2?1, which contain 0?095 kg
Ca/ton steel, are indicative of a degree of over
modification due to large amount of Ca addition to
these heats. This gives a possibility that the injected Ca is
more likely to react with the evenly distributed dissolved
sulphur. Nearly all CaS inclusions formed were asso-
ciated with Ca–aluminate which indicates that the
wetting of CaS by liquid inclusions makes it less likely
to cause SEN clogging during casting process. The Ca–
aluminate inclusions have a higher capacity of absorbing
sulphur.8
The concentration of sulphur in equilibrium with Ca–
aluminate inclusions can be very high and therefore,
absorb most of the sulphur present in the steel melt.
During the cooling and steel solidification, the solubility

Table 7 Chemical analysis of Ca and S for ladle (LRF) and tundish (TD) samples

Ca in LRF and TD, ppm S in LRF and TD, ppm

LRF TD LRF TD CaS, %

1.1 31 24 19 10 6.48–41.02
1.7 18 14 12 10 0.05–7.61
2.1 32 22 23 15 4.21–34.83
2.2 23 18 69 65 1.26–4.50
2.3 23 17 17 13 0.77–2.61

Ironmaking and Steelmaking 2009 VOL 36 NO 6 439

Abdelaziz et al. Ca addition for improved cleanness of LCAK steel

a heat 1?1 type A (LRF sample); b heat 2?3 type A (LRF sample); c heat 2?2 type A (tundish sample); d heat 2?3 type A
(tundish sample)
5 SEM images for Ca–aluminate inclusions

of the sulphur in the Ca–aluminate inclusion decreases
and precipitates in a ring form of CaS, around nucleus
of Ca–aluminates.19 As the solubility of Ca in the steel
decreases with decreasing steel temperature, it can react
with the sulphur on the surface of Ca–aluminate
inclusions to form superficial layers of CaS present
around these inclusions, which explains CaS formation
in tundish samples of heats 1?1 and 2?3 when the
temperature decreases from 1590 to 1555uC.
From Table 7 and Fig. 7, it can be seen that Ca
addition to liquid steel is the main factor of CaS

6 Distribution of analysed CaS contents (wt-%) of modi-

fied inclusions found in LRF samples (heats 1?1 and 7 Distribution of analysed CaS contents (wt-%) of modi-
2?3) fied inclusions found in tundish (TD) samples

440 Ironmaking and Steelmaking 2009 VOL 36 NO 6


8 Relationship between Ca (kg/ton steel) added per heat
and sulphur drop (ppm) in melt (differ)
formation. The concentration of CaS for high
(S569 ppm) or low sulphur (S517 ppm) content steel
ranges from 0?77 to 4?5% for 0?06 kg Ca/ton steel.
However, increasing the Ca addition to 0?095 kg/ton
steel leads to an increase in the CaS from 4?21 to
41?02 kg/ton steel for low sulphur content steel.
Figure 8 shows the correlation between the Ca
amount added to the steel bath and the sulphur drop
between ladle and tundish (LRF–TD) (Table 8). As
shown in this figure, as the amount of Ca (kg/ton steel)
increases, the difference between the sulphur content
before Ca added in LRF and S content in tundish
increase. This increase in difference indicating drop in
sulphur content is independent on the sulphur content
(in current study, as seen from Table 7) but dependent
on the Ca amount (kg) added to the steel bath.
Conclusions
In this work, trials were made on two sequences (14
heats) to reach the minimum Ca addition possible for
preventing SEN clogging and for improving the steel
cleanness. The conclusions that can be drawn from this
work are the following
1. SEN clogging was successfully prevented by
decreasing the amount of Ca addition from 0?095 to
0?06 kg/ton steel to modify the alumina inclusions to
liquid or partially liquefied globular shape Ca–aluminate
inclusions.
2. Ca–aluminate of composition C12A7.CaS fully
modified inclusions, Ca–aluminate of composition
CA.CaS, CA2.CaS partially modified inclusions and
Al2O3.MgO spinel were found in steel samples taken
from ladle.
Abdelaziz et al. Ca addition for improved cleanness of LCAK steel
3. Ca–aluminate of composition C12A7.CaS fully
modified liquid inclusions and Ca–aluminate of compo-
sition CA6.CaS, CA2.CaS and CA.CaS partially mod-
ified inclusions were found in steel samples taken from
tundish.
4. Ca addition to liquid steel is the main factor of CaS
formation. The concentration of CaS for high or low
sulphur content steel ranges from 0?77 to 4?5% for
0?06 kg/ton steel. However, increasing the Ca addition
to 0?095 kg Ca/ton steel leads to an increase in the CaS
from 4?21 to 41?02 kg/ton steel for low sulphur content
steel.
5. Reducing Ca addition has a significant effect on
decreasing the attack of tundish refractories and
consequently improves the steel cleanness.
References
1. L. F. Zhang and B. G. Thomas: Proc. 7th European Electric
Steelmaking Conf., Venice, Italy, May 2002, AIM, 2?77–2?86.
2. A. W. Cramb: ‘Inclusion formation and removal’, AFS, August
1998, available at: http://neon.mems.cmu.edu/afs/afs2/form.html
3. L. F. Zhang and B. G. Thomas: ISIJ Int., 2003, 43, (3), 271–
291.
4. R. Dekkers, B. Blanpain, P. Wollants, F. Haers, C. Vercruyssen
and B. Gommers: Ironmaking Steelmaking, 2002, 29, (6), 437–444.
5. R. Dekkers: ‘Non-metallic inclusions in liquid steel’, PhD thesis,
Katholieke Universiteit Leuven, Leuven, The Netherlands, 2002,
available at: http://www.mtm.kuleuven.ac.be/Personnel/RD/
inhoud/download_thesis.html
6. E. T. Turkdogan: ‘Fundamentals of steelmaking’, 245–296; 1996,
London, IOM.
7. L. F. Zhang and B. G. Thomas: Proc. XXIV National Steelmaking
Symp., Morelia, Mexico, November 2003, 138–183.
8. J. Carlos, S. Pires and A. Garcia: REM, Rev Esc. Minas, 2004, 57,
(3), 183–189.
9. D. Janke, Z. T. Ma, P. Valentin and A. Heinen: ISIJ Int., 2000, 40,
(1), 31–39.
10. E. T. Turkdogan and R. J. Fruehan: in ‘Fundamentals of iron and
steelmaking’, 11th edn, 13–157; 1998, London, IOM.
11. L. Holappa, M. Hämäläinen, M. Liukkonen and M. Lind:
Ironmaking Steelmaking, 2003, 30, (2), 111–115.
12. G. J. W. Kor and P. C. Glaws: in ‘Fundamentals of iron and
steelmaking’, 11th edn, 661, 713; 1998, London, IOM.
13. C. Espinosa: ‘Evolution of non-metallic inclusions in the refining
process of steel’, Master thesis, University of Buenos Aires, Buenos
Aires, Argentina, 2005.
14. K. Beskow, J. Jia, C. H. P. Lupis and D. Sichen: Ironmaking
Steelmaking, 2002, 29, (6), 427–435.
15. I.-H. Jung, S. Decterov and A. Pelton: ISIJ Int., 2004, 44, (3), 527–
536.
16. B.-H. Yoon, K.-H. Heo, J. S. Kim and H.-S. Sohn: Ironmaking
Steelmaking, 2002, 29, (3), 215–218.
17. S. Abdelaziz: ‘Effect of calcium addition on the cleanliness of low
carbon Al-killed steel’, Master thesis, Cairo University, Cairo,
Egypt, 2006.
18. J. M. A. Geldenhuis and P. C. Pistorius: Ironmaking Steelmaking,
2000, 27, (6), 442–449.
19. K. Larsen and R. J. Fruehan: ISS Trans., 1991, 12, 125–132.
Ironmaking and Steelmaking 2009 VOL 36 NO 6 441