Ironmaking & Steelmaking

Processes, Products and Applications

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Optimisation of ladle slag composition by

application of sulphide capacity model

M.A.T. Andersson, P.G. Jönsson & M. Hallberg

To cite this article: M.A.T. Andersson, P.G. Jönsson & M. Hallberg (2000) Optimisation of ladle
slag composition by application of sulphide capacity model, Ironmaking & Steelmaking, 27:4,
286-293, DOI: 10.1179/030192300677570

To link to this article: http://dx.doi.org/10.1179/030192300677570

Published online: 18 Jul 2013.

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Optimisation of ladle slag composition by
application of sulphide capacity model
M. A. T. Andersson, P. G. Jönsson, and M. Hallberg

Royal Institute of Technology (KTH)7–9 to calculate the

The sulphur distribution ratio for ladle slags at
Ovako Steel AB has been determined by calculating
the sulphide capacity using the Royal Institute of
Technology (KTH) model and the alumina activity
via an empirical expression suggested by Ohta
and Suito, and by using the well established
theories for sulphur refining. A parameter study
was carried out based on plant data from a previous
study on desulphurisation. The effect of carbon and
aluminium in the steel, the temperature of the steel,
and alumina and lime in the slag on the sulphur
distribution ratio was investigated. It was shown
that the Al O /CaO ratio had the largest influence
2 3
on the conditions studied, and that when it
increased the sulphur distribution ratio decreased.
Based on these results, new plant trials were
carried out, in which the alumina content in the slag
was changed. The calculated sulphur distribution
ratios for these trials were found to be in good
agreement with experimentally determined sulphur
distribution ratios. It is concluded that the present
approach can be used to optimise multicomponent
ladle slags with respect to sulphur refining.
I&S/1493
Dr Andersson and Professor Jönsson are in the Department of
Metallurgy, Royal Institute of Technology, S–100 44 Stockholm,
sulphide capacity of the ladle slags. The selection of this
approach is based on results from an earlier study,10 in
which several models and relationships were used to predict
the alumina activity in the slag, oxygen activity in the steel,
sulphide capacity of the slag, and sulphur distribution.
In the first part of the present paper, the theories behind
the model approach to predict the sulphide capacity and
sulphur distribution are outlined. Thereafter, the plant
trials at Ovako Steel are described. Then a study focusing
on some parameters that affect sulphur refining is presented.
The parameter study was based on plant data from an
earlier paper by the present authors.10 Finally, the results
from new plant trials are discussed. These plant trials were
planned based on the results of the parameter study.
THEORETICAL BACKGROUND
When discussing sulphur refining during steelmaking the
following important exchange reaction should be considered11
DS (g)+(O2−) =DO (g)+(S2−) . . . . . (1)
2 slag 2 slag
Reaction (1) describes the favourable equilibrium between
the slag phase and the gas phase with respect to sulphur
and oxygen at partial pressures of oxygen less than 10−6 atm,
a condition generally fulfilled during ladle treatment of
molten steel. The equilibrium constant for reaction (1)
could be expressed as

A B
Sweden, and Tech. Lic. Hallberg is with Ovako Steel AB, S–813 82 a p 1/2
Hofors, Sweden. Manuscript received 1 December 1999; accepted K = S2− O2
24 February 2000. 1 a p
O2− S2

A B
© 2000 IoM Communications Ltd. f (%S) p 1/2
= S2− slag O2 . . . . . . . . . (2)
a p
O2− S2
where a and a are the activities of sulphur and oxygen
S2− O2−
INTRODUCTION in the slag phase, p and p are the partial pressures of
S O2
At Ovako Steel it has been known for many years that the S (g) and O (g), f 2 is the activity coefficient of sulphur
2 2 S2−
fatigue strength of the ball bearing steel is improved if in the slag phase, and (%S) is the sulphur content of the
slag
the total oxygen content (the amount of oxide inclusions) slag in wt-%.
is lowered. Therefore, this has been the focus of many The sulphide capacity C was defined by Fincham and
S
individual projects, resulting in a reduction of the average Richardson12 using equation (2)
total oxygen content from 11 ppm in 1985 to 5 ppm in K a
1996.1 It is also known that it is important to keep the size C = 1 O2−
S f
of oxide inclusions lower than 18 mm, since larger inclusions S2−

may initiate cracks.2 As a result, several investigations have
been conducted to study inclusion size during bearing steel
production.3–5 Thus, a fairly good understanding exists of
the variation of oxide inclusion content during production
and the effect on the material properties of bearing steel.
Now, attention has shifted to controlling the amount of
sulphur in the steel. The reason for this is that interest in
sulphides as crack initiators has increased since reduction
of the amount of oxide inclusions has been achieved.
The work documented in the present paper focuses on
the thermodynamic aspect of sulphur refining during vacuum
degassing of ballbearing steel grades. The sulphur distri-
bution between slag and steel is predicted by calculating
the alumina activity in the slag from an empirical expression
suggested by Ohta and Suito,6 then using these data to
calculate the oxygen activity in the molten steel, and finally
applying a model developed at the Department of Metallurgy,
286 Ironmaking and Steelmaking 2000 Vol. 27 No. 4
A B
O 1/2
p
=(%S)
slag p 2
. . . . . . . . . . (3)
S2
where K is the equilibrium constant for equation (1).
1
The sulphide capacity is a property of the slag, which is
dependent only on the temperature and the slag com-
position. It describes the potential ability of an arbitrary
homogeneous molten slag to remove sulphur, and it could
be used to compare the desulphurisation characteristics of
different slags.
Several models have been developed to estimate how the
sulphide capacity of a slag varies with composition and
temperature. Some of these models have been evaluated by
the present authors in an earlier publication.10 The most
useful is a model for calculation of the sulphide capacity for
slags at different temperatures, developed at the Department
of Metallurgy, Royal Institute of Technology, referred to as
ISSN 0301–9233
 Andersson et al. Optimisation of ladle slag composition 287

the KTH model.7–9 The KTH model enables the prediction
of the sulphide capacities of multicomponent slags from
the data of lower order systems. In earlier studies carried
out within the Department of Metallurgy, experimental
data for sulphide capacities from laboratory experiments
have been used to verify model predictions of ternary,7
quaternary,8 quinary,8 and six component9 slag systems.
In the KTH model, the expression of sulphide capacity
from equation (3) is represented by the following relationships
A B
DGo
K =exp − . . . . . . . . . . . (4)
1 RT
and
C D
a ∑ (X j )+j
O2− =exp − i i mix . . . . . . . (5)
f RT
S2−
where, in equation (4), DGo is the Gibbs free energy of
reaction (1), T is the temperature, and R is the gas constant.
In equation (5), X is the molar fraction of component i in
i
the multicomponent system. The term j is expressed as a
i 2Al+3O
linear function of the temperature for each component in
the slag in the absence of interaction between different
species. The term j represents the mutual interaction
mix
( binary and ternary) between different species in the slag,
and is dependent on slag composition and temperature.
To express the mixing, the liquid slag is described by a
modified Temkin13 approach, which considers the mixing
In the present work, equation (11) was used to calculate
the equilibrium sulphur distribution L between slag and
S
steel. The sulphide capacity was first calculated using
the KTH model.7–9 The slag compositions used in the
calculations were normalised to a four component system
(Al O –CaO–MgO–SiO ).
2 3 2
The activity coefficient in equation (11) for the steel bath
is calculated using Wagner’s equation
log f = ∑ (ei [%i ]) . . . . . . . . . . . (12)
j j
where f is the activity coefficient for element j in the
j
molten steel, i represents the dissolved elements in the molten
steel, and ei is the interaction parameter for element j. The
j
interaction parameters in the present case were taken from
a publication by Engh.15
The oxygen activity in the steel bath a was calculated
O
by assuming that the dissolved aluminium and oxygen in the
steel bath and alumina in the top slag were in equilibrium,
according to
2 =Al O (s) . . . . . . . . . . . (13)
2 3
DGo=−1 205 115+386·714T (J mol−1) (14)
The data for the change of Gibbs free energy, equation (14),
were taken from a publication by Hayes.16 Solid alumina
was chosen as the standard state. Thus, the equilibrium
constant K for equation (13) could be written as
13

A B
of cations and anions within each of their subgroupings. −DGo
K =exp
More details regarding the equations and the assessed para- 13 RT
meters necessary for the calculation have been presented
elsewhere.7–9 a
= Al2O3 . . . . . . . . . . . . . . (15)
In the model, pure liquid FeO is chosen as the standard, a2 a3
for which the ratio a / f is taken to be unity. The value Al O
O2− S2− where a is the activity of alumina in the slag phase
of DGo is calculated from sulphide capacity measurements Al O3
and a is 2the activity of aluminium in the metal phase.
of pure liquid FeO as Al
To calculate the oxygen activity a from equation (15),
DGo=118 535−58·815T (J mol−1) . . . . . (6) O
the activities of aluminium in the molten steel and alumina
Once the sulphide capacity of a certain slag is known, the in the top slag need to be estimated. The activity of
equilibrium sulphur distribution L between slag and metal aluminium in the molten steel in equation (15) could be
S
can be calculated. The sulphur distribution is easier to use expressed as
in practice, as it can be directly measured as the quota a = f [%Al ] . . . . . . . . . . . . (16)
between the sulphur contents in the slag and the metal. To Al Al
enable the sulphide capacity to be related to the equilibrium where f is the activity coefficient of aluminium in the
Al
sulphur distribution between the slag and metal phases, the metal phase and [%Al ] is the aluminium content by weight
following reaction is introduced in the steel. The activity coefficient f was calculated using
Al
S2 +(O2−) =O 2 +(S2−) . . . . . . (7) equation (12).
metal slag metal slag The activity of alumina in the top slag in equation (15)
Reactions (1) and (7) are combined to give was more difficult to estimate owing to the lack of reliable
S2 +DO (g)=O 2 +DS (g) . . . . . . . (8) experimental data for the Al O –CaO–MgO–SiO system.
metal 2 metal 2 2 3 2
The equilibrium constant K is expressed as14 In the present work an empirical expression by Ohta and
8 Suito6 was used for estimation of the alumina activity.
935 Ohta and Suito6 used a slag–metal equilibrium technique to
log K =− +1·375 . . . . . . . . . . (9)
8 T determine the activity data at 1600°C. A multiple regression
The equilibrium constant K can also be written as analysis gave the following expression for the alumina
8 activity in the slag

A B
a p 1/2
K = O S2 [−0·275(%CaO)+0·167(%MgO)]
8 a p log a =
S O2 Al2O3 (%SiO )
(%S) a 2
= slag O . . . . . . . . . . (10) +0·033(%Al O )−1·560 . . . . . (17)
[%S] f C 2 3
metal S S where the slag composition is given in wt-%. The validity
where a and a are the activities of oxygen and sulphur
O S of Ohta and Suito’s expression has been discussed by the
in the metal phase, f is the activity coefficient for sulphur
S present authors in an earlier publication.10
in the metal phase, and [%S] is the sulphur content in
metal
the metal phase.
By combining equations (3), (9), and (10), the following PLANT TRIALS
expression for the equilibrium sulphur distribution L Process description
S
between the slag and metal phases is obtained14 Ovako Steel has a scrap based steel plant located in Hofors,
(%S) Sweden. The scrap is melted in a 100 t oval bottom tapped
log L =log slag
S [%S] (OBT) electric arc furnace. The raw steel is modified with
metal respect to the desired phosphorus, carbon, and temperature
935 levels before it is tapped into a ladle. The ladle refractory
=− +1·375+log C +log f −log a (11)
T S S O is carbon bound magnesite, and predeoxidation is done
Ironmaking and Steelmaking 2000 Vol. 27 No. 4
288 Andersson et al. Optimisation of ladle slag composition
1 Schematic diagram showing steel and slag sampling
during ladle refining operation
during the tapping. The ladle is then transported to an
ASEA–SKF ladle furnace (LF) station, where careful
deslagging of the furnace slag is done before the secondary
refining operation starts. The secondary refining operation
is carried out in three main steps. In the first step, a syn-
thetic slag mixture is added along with alloys and aluminium.
Graphite electrodes are used for melting the synthetic slag
formers and to compensate for heat loss. Induction stirring
is used for homogenisation of temperature and alloying
additions. In the second step, the steel is vacuum degassed
to remove hydrogen and sulphur. Inert gas stirring (argon)
through two porous plugs gives rise to a large surface area
between the argon bubbles and liquid steel, which is
beneficial for hydrogen removal. The intense stirring also
results in mixing of the molten steel and the slag, which
enhances the removal of sulphur. In the third step, induction
stirring is used to promote the separation of inclusions
from the molten steel to the top slag. Only mild induction
stirring is used, to minimise reactions between steel and
slag as well as reoxidation from the atmosphere. During this
final step, the steel and slag are also heated with electrodes
to obtain the correct casting temperature. If necessary, a
final adjustment of the steel composition by alloy additions
is also carried out. After the ladle treatment is finished, the
steel is cast into 4·2 t ingots by uphill teeming.
Experimental procedure
The results from the parameter study, described below,
indicated that the ratio of Al O /CaO in the slag has a
2 3
significant effect on the sulphur distribution ratio. Therefore,
plant trials were carried out for a high carbon and chromium
bearing steel grade (1 wt-%C and ~1·4 wt-%Cr), in which
the alumina content in the slag before vacuum treat-
ment was allowed to vary between 27 and 42 wt-%. The
other slag constituents varied during the trials as follows:
44–58 wt-%CaO, 4–11 wt-%MgO, and 6–11 wt-%SiO . In
2 In Fig. 2 an example of the change in slag composition
the trials, a commercial synthetic slag mixture was used
together with lime. In some cases ( high alumina slags) pure
alumina was also added to the slag. Note that these slag
compositions do not correspond to those used in normal
production.
Slag and steel samples were collected during ladle treat-
ment corresponding to the three main steps of the secondary
refining operation, illustrated in Fig. 1. The temperature of
the molten steel was measured at each sampling point.
Both the temperature measurements and the steel samples
were taken using the automatic sampling equipment at the
LF station. Slag samples were collected manually with a
slag spoon.
Analysis procedure
Slag analysis
Nearly the entire amount of each collected slag sample was
well ground, resulting in an evenly mixed powder from
which a portion could be taken for analysis. Metallic iron
particles were carefully removed from the ground slag
samples with a magnet. The slag samples were then analysed
using an X-ray fluorescence method (Siemens SRS 303) to
determine their oxide compositions. The relative analysis
Ironmaking and Steelmaking 2000 Vol. 27 No. 4
accuracy was ±3%. The slag samples were also separately
analysed for sulphur using a melting and combustion
method (Rosemount CSA 5003). The relative analysis
accuracy for this was also ±3%.
Steel analysis
The steel samples were analysed by optical emission spectro-
scopy (Bausch & Lomb, ARL OES 3560). The relative
analysis accuracy for the elements aluminium, chromium,
manganese, and silicon was within ±5%. Carbon and
sulphur contents in the steel samples were determined using
the fusing method (Leco CS-244). For carbon and sulphur
the relative analysis accuracy was ±0·7% and ±5·4%,
respectively.
RESULTS AND DISCUSSION
Parameter study
Based on plant data from a previous study10 the effect
of the following parameters on the equilibrium sulphur
distribution was calculated:
(i) %Al in the molten steel
(ii) %C in the molten steel
(iii) temperature
(iv) (%Al O )/(%CaO) ratio in the top slag.
2 3
It was concluded from the earlier investigation10 that the
components SiO and MgO in the top slag usually changed
2
very little during the ladle refining operation. Thus, suitable
contents of SiO and MgO were chosen and kept constant
2
during the calculations for the entire parameter study. A
typical bearing steel composition was chosen for the calcu-
lation, with the following major alloying elements: 1·4%Cr,
0·28%Si, and 0·28%Mn. The ranges of the other values
used are given in Table 1. The method of calculation is
outlined in the ‘Theoretical background’ section above.
Sulphide capacity
The variation in the sulphide capacity for an Al O –CaO–
2 3
8%MgO–7%SiO slag at different temperatures and Al O /
2 2 3
CaO ratios was calculated using the KTH model. The temper-
atures for which the calculations were done are given in
Table 1. The results from the calculations can be seen in
Fig. 2; the sulphide capacity decreases with an increase of
the ratio of %Al O /%CaO in the slag. A decrease in the
2 3
temperature also causes a decrease in the sulphide capacity.
Consequently, if the temperature decreases at the same
time as the Al O /CaO ratio increases, there will be an
2 3
additional effect on the decrease of the sulphide capacity.
and temperature from earlier trials at Ovako Steel10
during vacuum degassing is illustrated by an arrow moving
from point A to point B. It corresponds to a decrease of
temperature from 1600 to 1535°C and, at the same time,
an increase of the Al O content from 27 to 32% (see also
2 3
Table 2). In this hypothetical case the sulphide capacity
falls from ~0·004 to 0·0015, which is a remarkable decrease
of ~60%.
Carbon and aluminium in steel
In Fig. 3 the equilibrium sulphur distribution is shown as
functions of the carbon and aluminium contents in the
steel. During the calculations the slag composition was
fixed at 35%Al O , 50%CaO, 8%MgO, and 7%SiO . The
2 3 2
temperature was also fixed at 1550°C. From Fig. 3 it can
Table 1 Ranges of values used in parameter study
%C %Al %Al O
2 3
%CaO
in steel in steel T, °C in slag in slag
0·2–1·0 0·02–0·06 1500–1650 25–45 40–60
T temperature.

2 Calculated sulphide capacity as function of %Al O in
2 3
top slag and temperature: other slag components are
constant at 8%MgO and 7%SiO
2
be seen that the equilibrium sulphur distribution L increases
S changes from ~650 to 400, which is a decrease of ~38%.
if the carbon content in the steel increases. This is a result
of the positive interactions between carbon and sulphur
and aluminium and sulphur in the molten steel. The activity
coefficients of sulphur and aluminium f and f will
S Al
increase with an increased carbon content. The direct
influence of f on L can be seen in equation (11). An
S S
increase in f will lead to an increased aluminium activity
Al
and a decreased equilibrium oxygen activity in the molten
steel, which can be concluded from equations (15) and
(16). The decreased oxygen activity will also increase the
sulphur distribution according to equation (11).
An increase of the activity coefficient of aluminium will
decrease the oxygen activity in the molten steel, which
subsequently will increase L . A decrease of the aluminium
S
content in the molten steel will, on the other hand, cause
an increased oxygen activity, which will decrease L . As an
S
example, consider a change of aluminium content in the
molten steel during vacuum degassing from 0·06 to 0·03%,
as illustrated in Fig. 3 by an arrow moving from point A
3 Calculated equilibrium sulphur distribution as function
of carbon and aluminium contents in molten steel:
temperature is 1550°C and calculation assumes
35%Al O –50%CaO–8%MgO–7%SiO system
2 3 2
Table 2 Examples of changes during earlier plant trials10
Slag T, °C %Al in steel %C in steel
A (before degassing) 1600 0·06 1·0
B (after degassing) 1535 0·03 1·0
Andersson et al. Optimisation of ladle slag composition 289
4 Calculated equilibrium sulphur distribution as function
of carbon content and temperature in molten steel:
aluminium content is 0·04% and calculation assumes
35%Al O –50%CaO–8%MgO–7%SiO system
2 3 2
to point B. The carbon content is set to 1·0%. The
equilibrium sulphur distribution between slag and steel
Temperature and carbon in steel
Figure 4 shows the variation of the equilibrium sulphur
distribution with carbon content in the molten steel and
temperature. The slag composition was fixed and taken to
be the same as for Fig. 3. Also, the aluminium content in
the molten steel was fixed at 0·04%, while the temperature
and the carbon content were allowed to vary. In Fig. 4
it can be seen that L increases if the carbon content is
S
increased. (This is also observed in Fig. 3.) If the temperature
is decreased in Fig. 4, L increases, although the sulphide
S
capacity decreases (see also Fig. 2). This is caused by the
influence of the equilibrium constant for reaction (13), which
is dependent on the temperature (see equations (14) and (15)).
The equilibrium constant will increase with an increase in
temperature, which will decrease the oxygen activity in the
molten steel and, consequently, L will increase. In Fig. 4,
S
a decrease of temperature during vacuum degassing from
1600 (point A) to 1535°C (point B) is indicated. The carbon
content is 1·0%. In such a case the equilibrium L increases
S
from ~375 to 550 (an increase of ~47%).
Temperature and aluminium in steel
Figure 5 illustrates how changes in temperature and
aluminium content at a fixed slag composition and fixed
carbon content influence L . The carbon content is 1·0%
S
and the slag composition is the same as in Figs. 3 and 4.
It can be seen in Fig. 5 that decreases in aluminium content
and temperature have opposing effects on L . A decrease in
S
aluminium content decreases L , while a decrease in temper-
S
ature increases L . This is illustrated by the example of
S
vacuum degassing given in Table 2. The aluminium content
then decreases from 0·06 (point A) to 0·03% (point B),
while the temperature decreases from 1600 (point A) to
1535°C (point B). The total effect on L then is almost
S
negligible. It must be pointed out, however, that the total
effect on L depends very much on the specific case. If
S
the temperature reduction was greater and the aluminium
loss smaller than the above example, there would be an
obvious increase of the equilibrium sulphur distribution.
%Al O in slag %MgO in slag %SiO in slag
2 3 2
27 8 7
32 8 7
Ironmaking and Steelmaking 2000 Vol. 27 No. 4
290 Andersson et al. Optimisation of ladle slag composition
5 Calculated equilibrium sulphur distribution as function
of aluminium content and temperature in molten
steel: carbon content is 1% and slag composition is
35%Al O –50%CaO–8%MgO–7%SiO
2 3 2 2 3
Effect of Al O and CaO in top slag
2 3
The next step in the parameter study was to calculate the
effect of a changed Al O /CaO ratio on the equilibrium
2 3
sulphur distribution L . The results are presented in Figs.
S 2 3
6–8. In Fig. 6 the temperature and the aluminium content
in the molten steel were maintained at 1550°C and 0·04%,
respectively, while the Al O /CaO ratio and the carbon
2 3
content in the steel were allowed to vary. The MgO and
the SiO contents in the top slag were held constant at 8
2
and 7%, respectively. It can be seen that an increased
Al O /CaO ratio decreases L . This has two explanations.
2 3 S S
First, the sulphide capacity will decrease with an increased
Al O /CaO ratio (see Fig. 2). This will have a direct
2 3
negative effect on L in equation (11). Second, the activity
S 2 3
of Al O in the top slag will increase with an increased
2 3
Al O /CaO ratio, which will subsequently increase the
2 3
oxygen activity in the molten steel under equilibrium con-
ditions. An increased oxygen activity will also decrease L .
S
An increased carbon content in the molten steel increases
L because f and f increase, which is discussed above in
S S Al
connection with Fig. 3. It can be observed in Fig. 6 that
the influence of different carbon contents becomes more
negligible at a higher Al O /CaO ratio. In Fig. 6, the arrow
2 3
from point A to point B illustrates a change of Al O /CaO
2 3
ratio during vacuum degassing, from Table 2.
6 Calculated equilibrium sulphur distribution as function
of %Al O in top slag and carbon content in molten
2 3
steel: temperature is 1550°C, aluminium content in
molten steel is 0·04%, and other slag components are
constant at 8%MgO and 7%SiO
2 2
Ironmaking and Steelmaking 2000 Vol. 27 No. 4
7 Calculated equilibrium sulphur distribution as function
of temperature and %Al O in top slag: carbon and
aluminium contents in molten steel are 1% and 0·04%,
respectively, and other slag components are constant
at 8%MgO and 7%SiO
2
In Fig. 7 the effect of changes in temperature and Al O /
CaO ratio in the top slag on L is shown. The carbon and
S
the aluminium contents in the molten steel were fixed at
1·0% and 0·04%, respectively. It can be seen that L decreases
S
when the Al O /CaO ratio increases. (The reasons for this
2 3
are discussed above in connection with Fig. 6.) It can also
be seen that a decrease in temperature will increase L ,
S
which was observed in Figs. 4 and 5. The effect on L when
changing the temperature will be less if the Al O /CaO
2 3
ratio is high. The arrow in Fig. 7 from point A to point B
illustrates a change of both temperature and Al O /CaO
ratio during vacuum degassing trials, given in Table 2. It
shows that the decrease in L due to the increased Al O /
S 2 3
CaO ratio is partly compensated by the temperature fall
during the ladle treatment if the carbon and aluminium
contents are kept constant.
As a final summary of the work behind Figs. 2–7, a
case of variation in temperature, Al O /CaO ratio in the
2 3
top slag, and aluminium content in the molten steel was
investigated (Fig. 8). The carbon content was fixed at 1·0%.
The calculations were based on data given in Table 2. The
same data are used in Figs. 2–7 for generating the path
8 Calculated equilibrium sulphur distribution as function
of %Al O in top slag: case A, 1600°C and 0·06%Al and
2 3
case B, 1535°C and 0·03%Al; carbon content is 1%
and other slag components are constant at 8%MgO
and 7%SiO for both cases
 Andersson et al. Optimisation of ladle slag composition 291

from A to B. It can clearly be seen that the influence of a phase was calculated according to equations (14)–(16). The
change of aluminium content and temperature is almost activity coefficient for dissolved aluminium in the steel melt
negligible. The greatest influence of the studied parameters was calculated from Wagner’s equation (12). The results
is from an increase in Al O /CaO ratio in the top slag, are shown in Fig. 10, in which the estimated equilibrium
2 3
which decreases L during ladle treatment. It should be sulphur distributions are plotted against the sulphur distri-
S
stressed, however, that this conclusion is only valid if the butions from analysis of the slag and steel samples. It can
SiO content in the top slag is more or less constant. be seen that there was no equilibrium between the top
2
Plant trials Table 4 Analysis steel compositions (1 wt-%C and
1·4 wt-%Cr) and measured temperatures
As mentioned above, the main conclusion from the para-
meter study was that a change in the Al O /CaO ratio has Heat %Al %Mn %Si %S T, °C
2 3
the largest influence of the studied parameters on the sulphur
distribution ratio (see Fig. 8). Therefore, specific plant trials A-S1 0·039 0·27 0·24 0·020 1587
were planned in which the alumina content before vacuum A-S2 0·021 0·27 0·24 0·013 1530
A-S3 0·025 0·27 0·24 0·013 1532
treatment was allowed to vary between 27 and 42%. Since B-S1 0·064 0·28 0·29 0·020 1576
the slag needs to be used not only for sulphur refining but B-S2 0·047 0·28 0·29 0·014 1516
also for assimilation of inclusions and hydrogen refining, B-S3 0·044 0·28 0·29 0·015 1533
etc., larger variations of the alumina content were not C-S1 0·062 0·33 0·28 0·021 1565
C-S2 0·044 0·33 0·28 0·012 1497
allowed in the present trials. Moreover, the solubility of C-S3 0·040 0·33 0·28 0·011 1532
the magnesite refractory increases with an increase of the D-S1 0·065 0·29 0·26 0·020 1618
alumina content in the top slag.6,17 This was another reason D-S2 0·024 0·29 0·28 0·008 1552
for limiting the alumina content when deciding the top slag D-S3 0·035 0·29 0·28 0·008 1544
E-S1 0·043 0·26 0·24 0·017 1600
compositions. E-S2 0·022 0·26 0·24 0·012 1535
The results from the plant trials are presented in Tables E-S3 0·030 0·26 0·24 0·014 1533
3–5. First, to check whether the KTH model could describe F-S1 0·065 0·27 0·26 0·025 1582
the sulphur distribution qualitatively, the sulphur distri- F-S2 0·042 0·27 0·26 0·009 1534
F-S3 0·040 0·27 0·26 0·008 1537
butions determined from the plant trials were plotted G-S1 0·055 0·26 0·25 0·025 1597
against the calculated sulphide capacities (Fig. 9). Comparison G-S2 0·032 0·27 0·25 0·008 1526
between model and plant data shows that the sulphur G-S3 0·030 0·26 0·24 0·008 1541
distribution values from analysis increased with an increase H-S1 0·065 0·27 0·24 0·025 1606
H-S2 0·036 0·27 0·25 0·009 1528
in sulphide capacity. H-S3 0·035 0·27 0·25 0·009 1530
The equilibrium sulphur distribution L was then esti- I-S1 0·074 0·29 0·25 0·028 1573
S
mated for all heats using the above calculated sulphide I-S2 0·044 0·28 0·26 0·011 1514
capacities for the different slag samples. The oxygen activities I-S3 0·042 0·29 0·26 0·012 1537
J-S1 0·086 0·28 0·28 0·016 1580
were calculated in the following way. First, the activity of J-S2 0·051 0·27 0·29 0·007 1534
alumina in the top slag was estimated using the empirical J-S3 0·050 0·27 0·29 0·007 1537
expression of Ohta and Suito according to equation (17), K-S1 0·079 0·28 0·28 0·025 1583
and second, the equilibrium between dissolved aluminium K-S2 0·045 0·28 0·29 0·012 1520
K-S3 0·043 0·28 0·29 0·013 1536
and oxygen in the steel melt and the alumina in the slag

Table 3 Analysis slag compositions with normalised Table 5 Calculated sulphide capacities C and equilibrium
S
oxide composition sulphur distributions L
S
Heat %Al O %CaO %MgO %SiO %S Heat C L
2 3 2 S S
A-S1 36 45 8 11 0·64 A-S1 9·49×10−4 97·5
A-S2 36 41 12 11 1·2 A-S2 4·50×10−4 72·2
A-S3 37 41 11 11 1·2 A-S3 4·65×10−4 81·5
B-S1 42 45 6 7 0·61 B-S1 1·11×10−3 185·9
B-S2 44 42 7 7 1·3 B-S2 5·68×10−4 192·6
B-S3 44 41 7 8 1·2 B-S3 6·00×10−4 153·1
C-S1 41 45 7 7 0·63 C-S1 1·06×10−3 191·3
C-S2 42 43 8 7 1·6 C-S2 5·03×10−4 214·6
C-S3 43 42 7 8 1·4 C-S3 6·42×10−4 156·3
D-S1 36 49 6 9 0·30 D-S1 1·84×10−3 177·9
D-S2 42 44 8 6 1·6 D-S2 9·24×10−4 118·4
D-S3 42 44 8 6 1·5 D-S3 8·36×10−4 154·2
E-S1 42 47 5 6 0·43 E-S1 1·68×10−3 149·5
E-S2 43 42 8 7 1·2 E-S2 6·52×10−4 100·9
E-S3 44 41 8 7 1·2 E-S3 6·25×10−4 120·1
F-S1 28 58 7 7 0·73 F-S1 3·73×10−3 587·6
F-S2 32 54 7 7 2·6 F-S2 1·72×10−3 412·2
F-S3 32 54 7 7 2·7 F-S3 1·69×10−3 374·9
G-S1 27 57 8 8 0·74 G-S1 3·23×10−3 352·7
G-S2 30 51 9 10 2·0 G-S2 9·92×10−4 222·8
G-S3 30 51 9 10 2·0 G-S3 1·10×10−3 189·1
H-S1 38 53 3 6 0·36 H-S1 3·11×10−3 300·6
H-S2 44 46 5 5 2·7 H-S2 9·83×10−4 231·2
H-S3 44 46 5 5 2·3 H-S3 9·98×10−4 224·3
I-S1 36 46 11 7 0·57 I-S1 1·15×10−3 205·3
I-S2 39 42 13 6 2·0 I-S2 5·40×10−4 177·2
I-S3 39 42 13 6 2·0 I-S3 6·56×10−4 150·9
J-S1 38 46 10 6 0·54 J-S1 1·27×10−3 240·2
J-S2 41 39 16 4 1·6 J-S2 7·33×10−4 202·5
J-S3 42 40 14 4 1·6 J-S3 7·64×10−4 199·0
K-S1 38 45 9 8 0·65 K-S1 1·11×10−3 190·4
K-S2 43 41 9 7 1·7 K-S2 5·71×10−4 176·2
K-S3 42 41 10 7 1·6 K-S3 6·34×10−4 151·7

Ironmaking and Steelmaking 2000 Vol. 27 No. 4

292 Andersson et al. Optimisation of ladle slag composition
9 Analysis determined sulphur distribution between
slag and metal plotted against calculated sulphide
capacity (KTH model): slag samples were taken after
final heating and stirring period (S3)
10 Calculated equilibrium sulphur distribution plotted
against sulphur distribution determined from slag
and steel analysis
slag and the molten steel with respect to sulphur, before
degassing. Just after degassing, the estimated equilibrium
sulphur distributions agreed well with the sulphur distri-
butions determined by analysis. The agreement even some-
what improved after the final heating and stirring period
at the end of ladle treatment.
In Fig. 11 the heats were divided into two groups:
basicity <6·0, and basicity >6·0. Basicity is here defined
11 Calculated equilibrium sulphur distribution as function
of analysis determined sulphur distribution after final
heating and stirring period
Ironmaking and Steelmaking 2000 Vol. 27 No. 4
as the quota between %CaO and %SiO . The estimated
2
equilibrium L values were plotted against the analysis
S
sulphur distributions after the final stirring and heating
period at the end of ladle treatment. The heats with a
lower top slag basicity generally showed lower sulphur
distributions than the high basicity slags, except for one
heat. This heat also had the lowest Al O content of all
2 3
heats in addition to the lowest (%Al O )/(%CaO) ratio,
2 3
including heats with both high and low basicities.
It can also be noted that the demands of Ovako Steel
on the limits of sulphur content in the steel were always
fulfilled during the trials, although in many cases the slag
composition was not optimal for sulphur refining.
CONCLUSIONS
A model for calculation of sulphide capacities of multi-
component slags was earlier developed at the Royal Institute
of Technology (KTH).7–9 This model has been used together
with Ohta and Suito’s expression for alumina activity6
(to calculate the oxygen activity) to investigate which para-
meters affect the sulphur distribution ratio most when
desulphurisation is carried out during vacuum degassing in
an ASEA–SKF ladle furnace. Based on results from an earlier
study of desulphurisation,10 the carbon and aluminium
contents in the steel, the temperature of the steel, and the
alumina and calcium oxide contents of the slag were chosen
as variables. The other parameters that were held constant
during the calculations were taken from plant data.10 The
parameter study showed that the Al O /CaO ratio had the
2 3
greatest influence on the sulphur distribution for the studied
conditions. When it increased, the sulphur distribution ratio
decreased. This is mainly because of a decreased sulphide
capacity and an increased oxygen activity.
Based on the results of the parameter study a new set of
plant trials were carried out, in which the alumina content
in the slag before vacuum degassing was varied between 27
and 42%. Thereafter, the sulphur distribution ratio was
calculated in the same manner as described for the para-
meter study. The predicted values were found to agree very
well with the experimentally determined sulphur distri-
bution ratio values for the slag samples taken after vacuum
degassing. The calculated sulphur distribution ratios were
also found to increase with an increased sulphide capacity,
as expected from the theory of sulphur refining.
The overall conclusion from the present study is that the
suggested concept of calculating the sulphur distribution
ratio (using the KTH model to calculate the sulphide
capacity and Ohta and Suito’s expression to calculate the
alumina activity) has the two following important practical
applications.
1. It allows for fast and easy evaluation of the theoretical
desulphurisation conditions for the current refining praxis.
This is possible to do even for ladle slags with up to six
components, as that is the present limit of the KTH model
for the prediction of sulphide capacities.
2. It makes it possible to determine theoretically which
parameters have the greatest influence on the equilibrium
sulphur distribution ratio. Thereafter, the top slag com-
position can be optimised with respect to desulphurisation
for each major steel grade produced.
ACKNOWLEDGEMENTS
The authors wish to thank Dr M. Nzotta, M. Göransson,
U. Leray, and personnel at the ladle furnace station at
Ovako Steel AB for their assistance during the plant trials.
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