j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5

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Original Article

Reaction between molten steel and

CaOeSiO2eMgOeAl2O3-FetO slag under varying
amounts of converter carryover slag

Shen-yang Song***, Jing Li*, Wei Yan**

State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing, 100083, China

article info abstract

Article history: Converter carryover slag during tapping has been a trouble for improvement of steel
Received 22 November 2021 quality. In order to give an insight into the action mechanism of carryover slag on steel
Accepted 27 January 2022 during tapping, a serious of molten steel-slag reaction experiments was conducted to
Available online 3 February 2022 elucidate the reaction mechanism between 3% Al steel and CaOeSiO2eMgOeAl2O3-FetO
type slag at 1600
C as well as its resulting effect on cleanliness under varying amount of
Keywords: converter carryover slag was investigated in laboratory. Composition evolutions in molten
Carryover slag steel and slag during the reaction and microstructure on the steel-slag interface were
Converter tapping investigated by employing different experimental techniques. 2[Al] þ (Fe2O3) ¼ 2
Aluminum deoxidation [Fe] þ (Al2O3) and 4[Al] þ 3(SiO2) ¼ 3[Si] þ 2(Al2O3) were confirmed as a major reaction in the
Reaction mechanism system. The initial (Fe2O3) content in experiments increased from 3% to 15%. The results
Desulfurization indicated the metal-slag reaction tended to stable after about 10 min, the mass transfer of
Inclusion [Al] in molten steel was the rate-controlling step [Als] was more prone to react with (SiO2)
for slags with initial (Fe2O3) less than 4.07%, but it reacted with both (Fe2O3) and (SiO2) when
(Fe2O3) content was more. It was therefore suitable addition of Al alloy should take (SiO2)
into consideration in addition to (Fe2O3) and dissolved [O]. Increase of carryover slag
amount represented by increase of initial (Fe2O3) decreased the sulfur distribution but
promoted the formation of MgO$Al2O3 inclusion. The sulfur distribution ratio decreased
from roughly 5000 to 2000 but the number density of inclusion increased from 22.125/mm2
to 45.875/mm2 with increase of initial (Fe2O3) from 3% to 15%.
© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

climbing. Since the improvement of the steel products quality

1. Introduction could not be achieved without the more refined management
of steel plant, the amount of converter carryover slag has
Given to the rough environment where steel products are al- gradually become a target of the corporation management [1].
ways used, the quality requirements for them have kept The reason why the amount of converter carryover slag

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: 657103886@qq.com (S.-y. Song), lijing@ustb.edu.cn (J. Li), weiyan@ustb.edu.cn (W. Yan).
https://doi.org/10.1016/j.jmrt.2022.01.154
2238-7854/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5
should be strictly controlled is that the converter final slag
includes about 15e25% (FeO) and 5% (MnO) [2e4]. The high
oxide slag is not conducive to deoxidation and desulfurization
in the subsequent secondary refining process [5,6].
At present, there are two deoxidizing strategies during
tapping process with regard to the aluminum deoxidizing
steel: dissolved oxygen concentrations in the metal increases
with progress of the converter blowing as the concentration of
[C] content decreases [7](1) the dissolved oxygen content in
the steel is calculated according to the CeO equilibrium curve,
and the amount of [Al] particles is just enough to decrease the
dissolved oxygen content in molten steel to 0%; (2) the dis-
solved oxygen content in steel is calculated according to the
CeO equilibrium curve. Due to the application of converter
slide plate facilities in the steel plant, the converter carryover
slag is assumed about 1500 kg by default during the tapping
process. In the last strategy, the addition of [Al] particles does
not only decrease the dissolved oxygen content in the steel to
0%, but also reduces the (FetO) content in the final converter
slag to less than 1%. However, in the case of the same
standard-type steel refining process, despite of the same
converter final slag composition and the unified addition
amount of [Al] particles after the converter, the [Als] content of
molten steel at the refining station inlet is still very different.
The reason is that the amount of converter carryover slag is
not measured accurately, although there are some methods to
decrease the carryover slag such as application of converter
slide plate facilities and infrared automatic detection of slag
amount [8]. This will cause incomplete deoxidation or excess
dissolved [Al], and subsequently the difficult control of in-
clusions and narrow steel compositions. Despite that some
methods to reduce converter carryover slag have been adop-
ted, it is still necessary to study the reaction mechanism be-
tween molten steel and slag in the tapping process in order to
give deep insight into the evolution process of slag to evaluate
the effect of carryover slag. The reaction between molten steel
and slag in the secondary refining has been reported widely.
Yu [9] studied the secondary oxidation of dissolved [Al] by
CaOeAl2O3eSiO2eMgOeFeO slag system under weak stirring
condition in the laboratory. By studying the influence of
different RH refining slag content on the molten steel and slag
reaction, as well as the influence of CaO/Al2O3 and (FetO)
content in slag, it concluded that the [Als] in molten steel
might continue to decrease until the (FetO) in slag was
completely consumed. However, the research focused on the
RH refining process, which has less reference significance for
the tapping process. Kim [10,11] studied the reaction between
[Als] and (FetO) (SiO2) in the flux under [Als]<1.8% condition.
But the flux components were completely different with
converter final slag. These research results could be hardly
applied in tapping process. Sun and Mori [12] studied the re-
action between Al-containing steel ([Als] ¼ 0.25e0.4%) and
CaOeSiO2eAl2O3-FetO-MnO slag with carrying (FetO) (SiO2)
and MnO). It concluded that the reaction rate of (FetO) and
Table 1 e Compositions of experimental steel (wt. %).
C Mn Si P S
0.129 1.59 0.35 0.0043 0.0030
1965
(MnO) with [Al] was higher than that of (SiO2) with [Al]. But
their research result still had limitations. The reaction order of
different compositions in the slag was not given. From the
above content, it can be seen that even though some re-
searchers have studied the metal-slag reaction in various
refining process, their findings cannot reveal the metal-slag
reaction of [Al] and CaOeSiO2eAl2O3-FetO-MgO slag system
under different carryover slag weights during converter tap-
ping process.
In this context, laboratory-scale experiments were con-
ducted to probe into the metal-slag reaction between [Als] and
CaOeSiO2eAl2O3-FetO-MgO slag system under different
amounts of converter carryover slag in the interface between
converter steelmaking and ladle furnace refining. Following
the evolution of slag compositions, the limiting step and
sequence of metal-slag reaction were determined. Finally,
according to the experimental results, the slag composition
prediction of converter tapping process was put forward and
improvement measures were advised for the steel company
operation.
2. Experiments
2.1. Steel sample preparation
Five steel bars with same weight about 200 g were cut from an
aluminum killed steel billet by wire cutting machine. The steel
bar was polished by a grinder until there was no stain point on
the surface and then the bar was washed using alcohol, after
that steel compositions were detected by a direct-reading spec-
trometer. The contents of O and N were analyzed through an O/
N/H analyzer. The steel compositions were shown in Table 1.
2.2. Slag sample preparation
Varying amounts of converter carryover slag with the same
slag compositions carryover is essential to conduct the
experiment. However, in order to ensure the safety of the lab
experiment, the actual volume of the slag and steel was
required to be less than 1/3~1/2 of the crucible. Therefore, the
above experimental settings could not provide a large weight
range of slag. There was another shortage of this experimental
setting, namely, tube furnace could not provide a good stirring
condition due to the limitation itself. When the amount of slag
was large, the height of slag layer would increase accordingly.
As a result, the molten steel and slag layer could not fully
contact and the accuracy of this experiment may be influ-
enced. The oxidation ability of the slag was judged by the total
(FetO) weight. High amount of the carryover slag had high
oxidation ability because it contained more (FetO) weight
under the same slag composition compared with the low
amount of carryover slag. Hence, same amount of carryover
slag with different (FetO) contents were designed in the
Al Ca Mg O N
0.018 <0.0005 <0.0005 0.0012 0.0029
1966 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5

the steel samples were taken out by F12  800 mm quartz tube
Table 2 e Designed slag composition (wt. %).
at 1min, 3min, 5min and 10min since the pre-melted slag was
Slag CaO SiO2 Fe2O3 Al2O3 MgO added for composition analysis. The tube furnace was cooled
1# 58.5 15.9 3.2 15.9 6.4 after the sampling process. The steel and slag cooled to room
2# 57.3 15.6 5.2 15.6 6.2 temperature along with the furnace were viewed as the cor-
3# 54.5 14.9 9.9 14.9 5.9 responding end point samples Steel samples were polished by
4# 55.5 20.2 15.2 3.0 6.1
a grinding machine with 60, 180, 360, 800, 1200, 2000 mesh
sandpapers until the surface was cleaned.

experiment to achieve different oxidation ability. The

2.4. Analysis and detection
increasing (Fe2O3) content in slag 1# to 4# in Table 3 represents
increasing oxidation with increase of carryover slag amount.
The compositions of steel were measured by direct reading
In this experiment, considering the change of slag
spectrometer (Thermo Fisher ARL-8860, USA). The oxygen and
composition from converter end point to ladle refining inlet,
nitrogen in steel were analyzed by oxygen/nitrogen/hydrogen
the deoxidization of molten steel and metal-slag reaction in
analyzer (EMIA-920V2, HORIBA, Japan). The sulfur content
the tapping process were studied by designing the same
was analyzed by a carbon sulfur analyzer (EMGA-830, HORIBA,
amount of slag but different slag composition. The design slag
Japan). The composition of [Als] and [Mn] in steel was
composition used in the experiment was shown in Table 2.
measured by an inductively coupled plasma mass spectrom-
Analytical reagent CaO(98.0mass%), MgO (98.5mass%),
eter (ICP-MS, USA). The composition of slag was measured by
SiO2 (99.0mass%), Al2O3(99.9mass%) and Fe2O3 (98.0mass
X-ray fluorescence (XRF, AxiosmAX, Holland). A scanning
%) were used to prepare the slag in Table 2. The mixed slag
electron microscope (SEM) (FEI Quanta-250; FEI Corporation,
sample was melted in an electrode graphite crucible (ID76m-
Hillsboro, OR) was used to observe the surface morphology of
m,OD91mm,H110mm) at 1500 OC. After that, the crucible was
metal-slag reaction, an energy dispersive spectrometer (EDS)
taken out quickly and the slag was poured into the ice-water
(XFlash 5030; Bruker, Germany) was used to analyze the re-
mixture for rapid cooling. Finally, the pre-melted slag was
action interface composition and the longitudinal section of
dried. The compositions of pre-melted slag were shown in
the steel after the reaction.
Table 3. It can be seen from Tables 2 and 3 that the compositions
of pre-melted slag are very close to that of the designed slag.

3. Results and discussion

2.3. Experimental process

3.1. Evolution of steel and slag compositions with

The schematic diagram of experimental facility was shown in
amount of carryover slag (oxide-ability of slag)
Fig. 1. A MgO crucible (ID62mm,OD71mm,H80mm) contained
200 g steel was put into the protective graphite crucible at first
The compositions of molten steel samples were shown in
and then they were put into the tube furnace and heated in
Table 4. It could be seen that [O] and [N] of the liquid steel did
high purity argon atmosphere. The temperature of the tube
not change significantly, which proved that the air tightness
furnace was measured by a B-type thermocouple and the
in the tube furnace experiment was good and almost no air
thermocouple connected with a PID (proportional-integral-
oxidation was detected in the experimental process. In the
derivative) controller. The heating rate of the tube furnace was



10 C/min below 1400
C and then was decreased to 5 C/min
when the temperature was above 1400
C. Once the furnace
was heated to 1600
C, it was held at 1600
C for 1 h with an
argon gas flow rate of 2.5 L/min for complete melting of steel
bar. After the steel was fully melted, 6 g Al particles with a
diameter less than 5 mm were added into the molten steel
through the observation hole with a F20  800 mm quartz
tube (the surface of the Al particles was waterless, stainless).
After 30 min, the steel sample was taken out by a
F12  800 mm quartz tube to make sure the [Al] homogeneous
in molten steel. Then 100 g pre-melted slag with a diameter
less than 10 mm was added into molten steel through the
observation hole with a F20  800 mm quartz tube. And then

Table 3 e Compositions of pre-melted slag (wt. %).

Slag CaO SiO2 Fe2O3 Al2O3 MgO
1# 59.4 15.8 2.9 15.2 6.8
2# 57.9 15.4 5.1 15.2 6.5
3# 54.4 15.7 9.4 14.2 6.3
4# 56.0 20.2 14.7 2.8 6.2
Fig. 1 e Schematic diagram of experimental facility.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5 1967

Table 4 e Composition changes of molten steel wt. %.

Test Sampling C Mn Si P S Al Ca Mg O N
time
1# initial 0.129 1.59 0.35 0.0043 0.0030 2.98 <0.0005 <0.0005 0.0012 0.0029
1min 0.132 1.50 0.71 0.007 0.0027 2.20 <0.0005 <0.0005 0.0010 0.0023
3min 0.135 1.52 1.53 0.010 0.0015 0.98 <0.0005 <0.0005 0.0011 0.0027
5min 0.150 1.48 1.96 0.012 0.0010 0.15 <0.0005 <0.0005 0.0011 0.0026
10min 0.166 1.45 2.07 0.011 0.001 0.020 0.0026 <0.0005 0.0010 0.0025
2# initial 0.129 1.59 0.35 0.0043 0.0030 2.80 <0.0005 <0.0005 0.0012 0.0029
1min 0.133 1.52 0.74 0.005 0.0027 2.02 <0.0005 <0.0005 0.0012 0.0025
3min 0.149 1.53 1.60 0.009 0.0013 0.82 <0.0005 <0.0005 0.0013 0.0025
5min 0.152 1.50 1.93 0.010 0.0013 0.16 <0.0005 <0.0005 0.0011 0.0025
10min 0.164 1.48 2.09 0.013 0.0012 0.020 0.0014 <0.0005 0.0011 0.0024
3# initial 0.129 1.59 0.35 0.0043 0.0030 2.97 <0.0005 <0.0005 0.0012 0.0029
1min 0.133 1.58 0.55 0.007 0.0022 1.72 <0.0005 <0.0005 0.0012 0.0031
3min 0.133 1.55 1.27 0.009 0.0018 0.32 <0.0005 <0.0005 0.0015 0.0030
5min 0.137 1.55 1.44 0.009 0.0016 0.033 <0.0005 <0.0005 0.0015 0.0029
10min 0.142 1.53 1.52 0.009 0.0015 0.022 0.0007 <0.0005 0.0015 0.0030
4# initial 0.129 1.59 0.35 0.0043 0.0030 2.90 <0.0005 <0.0005 0.0012 0.0029
1min 0.128 1.56 0.42 0.005 0.003 1.15 <0.0005 <0.0005 0.0014 0.0024
3min 0.136 1.54 0.62 0.007 0.0027 0.008 <0.0005 <0.0005 0.0014 0.0025
5min 0.144 1.54 0.93 0.006 0.0025 0.008 <0.0005 <0.0005 0.0014 0.0025
10min 0.144 1.55 1.30 0.006 0.0025 0.005 0.0010 <0.0005 0.0014 0.0024

composition of molten steel [C] and [Mn] remained basically continuously from Test 1# to Test 4#. It was preliminarily
unchanged [Ca] and [Mg] were trace quantities, and [Al] con- concluded that the reaction sequence of (Fe2O3) and (SiO2) in
tent decreased obviously. Correspondingly [Si] had a signifi- the slag with [Als] in the molten steel existed.
cant increase. By comparing the change of [S] content in a From the previous investigations of the present authors,
single furnace, it could be seen that the decrease of [S] content with regard to [Al], a reaction with silicon oxide is thermo-
resulted from desulfurization reaction. dynamically favorable [13,14]. Also, the reaction 2[Al] þ (Fe2-
The variation of slag composition was shown in Table 5. As O3) ¼ 2[Fe] þ (Al2O3) could happen in the experiment [10,11].
can be seen from Table 5, the content of (CaO) (MgO) in the Figure 4 indicated the SEM line scanning result of the
slag was stable during the whole reaction process. The con- metal-slag reaction interface at the Test 2# end point. It can be
tent of (Fe2O3) in slag decreased gradually, and the content of seen from the figures that the content of [Si] and [Al] were the
(SiO2) also decreased likewise. On the contrary, the content of highest at the interface, and then they decreased along the
(Al2O3) in slag increased continuously. boundary towards the inner direction of molten steel. This
Typical appearances of process slag samples were shown suggested that [Al] and reaction product [Si] would have a
in Fig. 2. It can be seen the slag color gradually changed from mass transfer in the steel-slag reaction layer.
black to white in the process from the initial pre-melting slag
to the experimental end point slag, which was consistent with
the decrease of the (Fe2O3) content. Table 5 e Variation of slag composition wt.%.
The composition changes of slag and molten steel during
Test Sampling CaO SiO2 Fe2O3 Al2O3 MgO
the metal-slag reaction were analyzed synthetically. The [Al] time
[Si] contents of molten steel and (SiO2) and (Fe2O3) contents in
1# initial 59.40 15.80 2.90 15.20 6.80
the slag during the experiment were plotted and shown in
1min 50.20 9.93 2.19 28.90 6.87
Fig. 3. 3min 51.04 6.80 1.42 29.30 6.03
As can be seen from the composition changes of molten 5min 51.00 5.70 1.19 29.50 6.00
steel in Fig. 3(a), even if the four groups of slag reacted under end 50.00 5.25 1.05 30.00 5.87
different slag conditions, the [Als] in molten steel decreased 2# initial 57.90 15.40 5.10 15.20 6.80
while the molten steel [Si] increased for all experiments and 1min 51.20 9.63 2.59 22.30 6.37
3min 51.04 5.80 1.33 28.60 6.33
then tended to be stable after 5 min. The difference between
5min 52.00 5.40 1.02 30.00 6.32
the four experimental groups laid in the [Als] decreasing rate
end 53.00 5.11 0.97 30.11 6.31
and [Si] increasing rate. 3# initial 54.40 15.70 9.40 14.20 6.30
In the metal-slag reaction, as shown in Fig. 3(b), the (Fe2O3) 1min 53.80 13.22 4.33 22.23 6.87
content of the initial pre-melted slag increased continuously 3min 52.74 6.80 1.41 29.30 6.03
from test 1# to 4# and then also tended to be stable after 5min 52.00 6.50 1.22 29.60 6.02
10 min. At the end of the reaction, all the content of (Fe2O3) in end 51.15 6.22 0.82 30.00 5.87
4# initial 55.60 20.20 14.70 2.80 6.20
the four groups of slag was less than or almost equal to 0.02%.
1min 50.20 19.82 7.19 6.10 6.87
From the experimental results of each test, the content of
3min 51.04 13.80 1.47 15.50 6.03
(SiO2) decreased with the experiment process, but it could be 5min 51.00 10.53 1.28 17.00 6.00
seen that the total (SiO2) reduction of slag decreased end 52.00 9.25 0.99 21.85 5.87
1968 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5

Fig. 2 e Typical appearance of process slag samples.

The SEM-EDS was used to conduct surface scanning anal- where [Al]o was the initial [Al]content in molten steel, [Al]eq
ysis on the metal-slag reaction interface from Test 1#. As can was the reaction equilibrium [Al] content in molten steel, KM
Al
be seen from Fig. 5, the coexistence of elemental [Si] and was the [Al] mass transfer coefficient, A was metal-slag
elemental [Al] proved the reduction reaction process of (SiO2) reaction area, rsteel was molten steel density, wsteel was
in slag by [Als] in the steel. molten weight.
If [Al]eq is small enough, the above equation can be
3.2. Consideration of reaction rate-controlling step changed to equation below:
m
According to the variation trend of molten steel and slag d½Al A$kAl $rsteel
 ¼ ½Alo (4)
composition under different amounts of carryover slag, the dt wsteel
two following reactions could occur at the metal-slag reaction If the oxide-reduction reaction of [Al] with slag on the
interface: metal-slag interface was the reaction rate-controlling step [Al]
oxidation reaction can be described as:
2½Al þ 3ðFet OÞ ¼ ðAl2 O3 Þ þ 3t½Fe (1)
Al ¼ Al þ3e
3þ
(5)
4½Al þ 3ðSiO2 Þ ¼ 2ðAl2 O3 Þ þ 3½Si (2)
According to the law of mass action, the rate equation can
Both of the above reactions can be represented by the be expressed as:
following process: (a) The [Al] in molten steel diffused from
the molten steel to the metal-slag interface; (b) [Al] had an dCAl
 ¼ kfAl $CAl  kbAl3þ $CAl3þ $C3e (6)
oxide-reduction reaction with (SiO2) or (FetO) in slag on the dt
metal-slag interface. f
where KAl was the forward reaction rate constant of Al; CAl
If [Al] diffused from molten steel to the metal-slag
was Al concentration, kbAl3þ was the forward reaction rate
interface was reaction rate-controlling step, then the
decrease rate of [Al] content in molten steel can be expressed constant of Al3þ; CAl3þ was Al3þ concentration; Ce- was the
as Eq. (3) [15]. electron concentration.
If the forward reaction rate above was fast enough to
d½Al A$kAl $rsteel

m
ignore the reverse reaction, then the above equation can be
¼ ½Aleq  ½Al0 (3)
dt wsteel abbreviated as:

Fig. 3 e Composition changes of molten steel and slag during the metal-slag reaction.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5 1969

Fig. 4 e SEM line scanning result of the metal-slag reaction interface.

d½Al app metal-slag was very fast. It is necessary to introduce the re-
 ¼ kAl $½Alo (7)
dt action activation energy into the study.
By comparing the aforementioned two reaction rate- The apparent reaction rate constant can be written as a
controlling steps, it could be found that these two rate equa- function of temperature and activation energy based on the
tions of control steps are all first-order rate equations, hence Arrhenius equation.
the logarithmic form of [Al] content in molten steel should  
Ea Ea
have a linear relationship with the reaction time. kapp =kapp
o ¼eexp  (10)
RT0 RT1
½Al0  ½Al app where k0
app
was the apparent reaction rate at temperature T0
ln ¼  kAl $t (8)
½Alo and T1 was the other reaction temperature.
The logarithmic form of the above equation could be
m
app A$kAl $rsteel expressed as:
kAl ¼ (9)
wsteel
 
Ea 1 1
app
where kAl was the apparent reaction rate. lnðkapp =kapp
o Þ ¼   (11)
R T0 T1
However, only the linear relationship between ln ([Al]0-
[Al])/[Al]o in steel was not enough to determine which is the According to the above analysis, the apparent reaction rate
reaction rate-controlling step, because Eq. (9) suited both two constant of the oxidation reaction of [Al] and its correspond-
control steps which were all first-order rate equations. ing activation energy can be calculated by Eqs. (8) and (11).
Therefore, further analysis was needed to clarify the real re- The relationship between the change of [Al] content with
action rate-controlling step. Due to the high temperature in reacting time was shown in Fig. 6. The decrease of [Al] in
steel-making process, the interface chemical reaction of this study at 1600
C was compared with the reported

Fig. 5 e Coexistence of elemental [Si] and elemental [Al] by SEM-EDS surface scanning analysis.
1970 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5
Fig. 6 e Decrease of [Al] in the experiments and kAl under
different temperatures [10,16].
results at different temperatures [10,16]. In this study, the
(Fe2O3) content of the initial pre-melted slag increased
continuously from Test 1# to Test 4# in metal-slag reactions,
but the [Als] decreasing rate was different. Initial [Als] con-
tents in four tests were all close to 3.0%, the contents of [Als]
were close to 1% in the Test 1# and Test 2# after reacting
3min. The content of [Als] was 0.32% in the Test 3# after
reacting 3min, but the content of [Als] was only 0.008% in
the Test 4# after reacting 3min. Almost [Als] in molten steel
at metal-slag surface has be consumed clearly and the
apparent reaction rate of [Als] in Test 4# at 0e3min was the
fastest. At 5 min [Als] in molten steel in Test 3 decreased to
0.033%, less than 0.1%. But the contents of [Als] were close to
0.15% in the Test 1# and Test 2# after reacting 5min. After
10 min, all the content of [Als] in the four groups of slag was
less than or almost equal to 0.02% and the metal-slag re-
action tended to stable after about 10 min. In the study of
Cho, the initial Al content in the liquid steel ([pct Al]0) was
low, and the ([pct Al]0) content was about 0.1%. When the
(pct CaO)/(pct Al2O3)>1.2, the calculated lines fitted the ex-
periments data, and the rate was also solely controlled by
mass transport of Al in the steel [17]. The study of Cho
supported the reaction processes when [Als] in molten steel
less than 0.1% in our study. The apparent reaction rate of Al
at 0e3 min ([Als]>0.1%) were higher than the apparent re-
action rate at 3e10 min ([Als]<0.1%) in Test 4#, hence the
experimental results of 0e3 min in Test 4# were fitted by a
straight line, and the experimental results of 3e10 min were
also fitted by the other straight line similarly. Also, the
experimental results of 0e5 min ([Als]>0.1%) in Test 3# were
fitted by a straight line, and the experimental results of
5e10 min ([Als]<0.1%)were also fitted by the other straight
line. It could be seen from Fig. 6 that temperature would
affect the apparent reaction rate, and the apparent rate
would be faster with increasing temperature [16]. Cho also
pointed out that when (pct Al2O3) > 40%, Mass transport of
(Al2O3) in slag may be responsible for the discrepancy seen
in the research of ln [pctAl]/[pctAl]0 with reaction time, but
(pct Al2O3) contents in our study were all under 30% [17].
In Fig. 6, R2 ¼ 0.977 in Test 1#, R2 ¼ 0.986 in Test 2#,
R ¼ 0.978 at 0e5 min and R2 ¼ 1 at 5e10 min in Test 3#,
2
R2 ¼ 0.965 in Test 4#. It indicated that the actual observation
point is closer to the predicted line when the value of R2
(determination coefficient) is closer to 1, and experimental data
fitted the linear regression. Robison and Pehlke [18] pointed out
that the activation energy of mass transfer of elements in
molten steel and slag was less than 84 kJ/mol and about 418 kJ/
mol, respectively. Generally speaking, the activation energy of
elements mass transfer in slag was lower than that in interface
reaction. According to the calculation, all activation energy in
the present study was less than 84 kJ/mol, and the average
activation energy was 50.84 kJ/mol. Therefore, mass transfer of
[Al] in molten steel was reaction rate-controlling step in this
study. Calculated mass transfer coefficients of Al when [Als]
>0.1% were higher than coefficients when [Als] < 0.1% in four
tests. The calculated mass transfer coefficient of Al was
0.87e1.24  104 m/s. This was agree well with that the mass
transport of Al in the steel controls the overall reaction at low Al
condition, as was reported by the present author [14].
3.3. Effect of (FetO) content in slag on [Al]-(SiO2) reaction
The evolution of slag compositions with reaction time under
different initial (Fe2O3) content was shown in Fig. 7.
It can be seen from Fig. 7 (a)e(d) that the (Fe2O3) content
decreases rapidly within 1 min in four tests with initial (Fe2O3)
increasing from 3% to 15%. As shown in Fig. 7 (a) and (b), the
(SiO2) content decreases rapidly within 1 min for slags with
initial (Fe2O3) less than 5%, but the decrease of (SiO2) signifi-
cantly slows down when the initial (Fe2O3) of slag is more than
5% according to Fig. 7 (c) and (d).
Furthermore, according to the change of (SiO2) with reaction
time in Fig. 7(e), It can be seen that DSiO2 values at 1 min for
slags with initial (Fe2O3) of 2.9% and 5.1% were almost same the
DSiO2 values at 3 min for slags with initial (Fe2O3) of 9.4% and
14.7%. This indicated that [Als] has stronger tendency to react
with (SiO2) for slags with initial (Fe2O3) content less than 5%.
In order to evaluate the effect of slag compositions on re-
action thermodynamics of reaction Eqs. (1) and (2), the DG of
these two reactions at 1600
C were calculated by Reaction
module of FactSage7.1 software, the relationship between
calculated DG and slag composition (SiO2) and (Fe2O3) was
plotted as show in Fig. 8.
As can be seen from Fig. 8, at 1600
C, DG of Eq. (1) is lower
when (SiO2) is 15% than that of Eq. (2) when (Fe2O3) is 5%,
which means that [Als] would be likely to react much stronger
with (SiO2) when the slag contained 15% (SiO2) and 5% (Fe2O3).
In order to further confirm the reaction order of [Al] with
(Fe2O3) and (SiO2), the Equilid module of FactSage7.1 software
was used to calculate the activity of individual component of
slag at 1600
C.
From the calculated activity shown in Table 6, it could be seen
that the (CaO) and (MgO) activities were almost the same at
1600
C in different experimental slag systems. The activity of
(Fe2O3) in the slag increased continuously with the increase of
(Fe2O3) content in the slag. The activity of (SiO2) in the slag was
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5 1971

Fig. 7 e Variation of slag composition under different initial (Fe2O3) (a) Fe2O3 ¼ 2.9%, (b) Fe2O3 ¼ 5.1%, (c) Fe2O3 ¼ 9.4%, (d)
Fe2O3 ¼ 14.7%, (e) decrement of (SiO2).

higher than that of (Fe2O3) for slag 1#, whereas the activity of 3.4. Effect of carryover slag amount (oxidability of slag)
(SiO2) in the slag was lower than that of (Fe2O3) for slag 2# despite on desulfurization
that two activities still have the same order of magnitude.
The next step was to find the slag composition when the Further analysis was needed to clarify whether slag compo-
activity of (Fe2O3) and (SiO2) in the slag was same at 1600
C. sition was conducive to refining desulfurization when it had
The slag systems contain 55% CaO, 6% MgO, 15% Al2O3, 15% been confirmed that the desulfurization reaction would occur
SiO2 and varying Fe2O3 were used for calculation at 1600
C. As [19e21]. The formula for calculating the sulfur distribution
shown in Table 7, when the activity of (SiO2) was equal to the ratio of the refining slag was as follows [20,21]:
(Fe2O3), the content of (Fe2O3) in the slag was about 4.07%.
ð%SÞ
Therefore [Al] reacts with (Fe2O3) preferentially when (Fe2O3) lgLS ¼ lg ¼ lgC0S þ lgfS  lgaO
½%S
is more than 4.07%, but it reacts with both (Fe2O3) and (SiO2)
935
when (Fe2O3) is less than 4.07%. This agrees well with the ¼ þ 1:375 þ lgCS þ lgf½S  lga½O (13)
T
aforementioned experiments that [Als] is more prone to react
with (SiO2) for slags with initial (Fe2O3) content less than 5%.
1972 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5

that high (Fe2O3) content of slag had a large disadvantage to

Fig. 8 e Relationship between DG and slag composition
(Fe2O3) and (SiO2) reacted with [Al] at 1600
C.
get high sulfur distribution ratio. The high content of (FetO)
in the slag was definitely caused by high amount of con-
verter carryover slag. Hence, it can be clarified that
decreasing the amount of carryover-slag was beneficial to
desulfurization.
An improved way of sulfur-distribution ratio in an actual
120 ton converter process was suggested in Fig. 9 (b). Com-
bined with the slag composition changes in Section 3.1, it
could be concluded that the sulfur-distribution ratio of con-
verter final slag was usually less than 10. The dissolved [O]
should be controlled below 500  106 and the carryover slag
should be limited less than 2000 kg. The 400 kg lime and 150 kg
Al particles were added in the furnace immediately during the
tapping process to de-oxidation. Finally, slag composition of
55e60% CaO, <6.5% SiO2, about 27% Al2O3, 6~8% MgO, <1.0%
Fe2O3 could be reached, and then a good desulfurization per-
formance was obtained.

n
RTðln Cs Þ ¼ 58:8157$T  118535  XAl2 O3 xAl2 O3 þ XCaO xCaO þ XMgO xMgO þ XMnO xMnO
2 O3 CaO Al2 O3 MnO Al2 O3 SiO2 MgOSiO
þXSiO2 xSiO2 þ xAl CaOSiO2 MnOSiO2
interaction þ xinteraction þ xinteraction þ xinteraction þ xinteraction þ xinteraction þ
2

Al2 O3 CaOSiO2 Al2 O3 MgOMnO Al O MgOSiO2 (14)

xinteraction xinteraction þ xFeOSiO
CaOFeO FeOMnO
interaction þ xinteraction
2
þ xinteraction þ xinteraction
2 3
þ
2 O3 MnOSiO2 Al2 O3 CaOMgO CaOMgOSiO MgOMnOSiO2 FeOMgOSiO
xAl
interaction þ xinteraction þ xinteraction 2 þ xCaOMnOSiO
interaction
2
þ xinteraction þ xinteraction 2
Al2 O3 FeOSiO2 FeOMnOSiO2 CaOFeOSiO2
þxinteraction þ xinteraction þ xinteraction

The KTH activity model was used to calculate the activity
of Al2O3 in the slag for desulfurization reaction, and the
Wagner model was used to calculate the activity coefficient of
[Als] and [S]. The specific methods were not described in
detail.
The influence of different amount of carryover slag on
sulfur distribution ratio was shown in Fig. 9.
It could be seen from Fig. 9 (a) that the test 4# containing
the highest (Fe2O3) had the lowest sulfur distribution ratio
during all the reaction process. It indicated clearly enough
3.5. Effect of carryover slag amount on inclusion
Control of inclusion is one of key contents during refining. In
order to make clear the effect of carryover slag amount on the
effect of inclusion, inclusion in endpoint steel samples after
reaction with slags with different initial (Fe2O3) content were
investigated. The acquired inclusion morphology on the
meta-slag interface is shown in Fig. 10.
As shown in Fig. 10, except for silicon produced by the
interaction reactions in test 1# and test 2#, MgO$Al2O3 as

Table 6 e Activity of individual components of initial slag at 1600
C.

Slag CaO SiO2 Fe2O3 Al2O3 MgO
1 5 5 4
1# 1.67  10 6.45  10 3.80  10 6.08  10 1.48  101
2# 1.67  101 6.37  105 9.02  105 5.41  104 1.48  101
3# 1.61  101 6.69  105 2.73  104 4.55  104 1.48  101
4# 1.66  101 6.72  105 1.22  103 5.54  105 1.48  101

Table 7 e Same activity of (Fe2O3) and (SiO2) in the slag at 1600
C calculated by FactSage 7.1.
slag activity slag activity
composition composition
CaO 55 1.67  101 55 1.67  101
SiO2 15 6.41  105 15 6.41  105
Fe2O3 4.06 6.40  105 4.07 6.42  105
Al2O3 15 5.71  104 15 5.71  104
MgO 6 1.48  101 6 1.48  101
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5 1973

Fig. 9 e Influence of slag and steel composition on sulfur capacity (a) sulfur distribution change of four tests (b) ideal process
operation in an actual 120 ton converter.

Fig. 10 e Inclusion at the endpoint steel samples after reaction with slags different initial (Fe2O3) (a) test 1# (b) test 2# (c) test
3# (d) test 4#.
1974 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5
Fig. 11 e Inclusion number density with different (Fe2O3)
content of initial slag.
primary inclusion can be seen from all endpoint steel samples
despite of initial (Fe2O3) content. MgO$Al2O3 spinel formation
has also been observed in steel grade that are in contact with a
well-deoxidized slag of high basicity, like those needed to
promote desulfurization [21].
After the inclusion specie was confirmed, 50 fields of view
with a total scanning area of 8 mm2 were randomly selected
under the SEM field. After that, the inclusion number density
was finally obtained and shown in Fig. 11. As can be seen from
Fig. 11, the number density of inclusion increases from 22.125/
mm2 to 45.875/mm2 with increase of initial (Fe2O3) from 3% to
15%, but no significant change of inclusion types was found.
The formation mechanism of MgO$Al2O3-type inclusions has
been studied by many researchers. The MgO$Al2O3-type in-
clusion was thought to be formed by the reaction between
Al2O3-type inclusions and [Mg] from the reduction of (MgO) in
the slag by Al [22e24]. Harada also pointed out that the
MgO$Al2O3 spinel-type inclusions could be observed soon
after Al addition [21,25]. The diffusion velocity of alumina
inclusion was depended on slag composition and slag vis-
cosity. He studied Al2O3 inclusion dissolved into tundish slag
[26], and the research in slag structure, physical and chemical
properties of slag was benefit to study the slag during tapping
process. In the present study, high initial (Fe2O3) content
means more addition of aluminum and more Al2O3 inclusions
generation, which will cause more MgO$Al2O3 inclusion. It is
therefore reduction of amount of converter carryover slag is
beneficial to further improvement of the steel cleanliness.
Moreover, the plant should also decrease (Fe2O3) content of
the converter final slag as much as possible.
4. Conclusions
Reaction between molten steel and CaOeSiO2eMgOeAl2O3-
FetO slag under varying amounts of converter carryover slag
was discussed, and the following conclusions could be made
based on the present study in this paper.
(1) Reaction between [Al] and slag during tapping tended to
be stable within 5min. High initial (Fe2O3) content would
prolong the time [Al] could react with (Fe2O3) preferen-
tially when (Fe2O3) was more than 4.07%, but it reacted
with both (Fe2O3) and (SiO2) when (Fe2O3) was more.
Mass transfer of [Al] in molten steel was reaction rate-
controlling step in this study according to the average
activation energy of 50.84 kJ/mol.
(2) The high (Fe2O3) content slag was disadvantage to the
high sulfur distribution ratio, and the high content of
(FetO) in the slag was definitely caused by high amount
of converter carryover slag. It was clarified that decrease
the amount of carryover slag was beneficial to the
desulfurization reaction.
(3) MgO$Al2O3 was primary inclusion for all endpoint steel
samples despite of initial (Fe2O3). The number density of
inclusion increases from 22.125/mm2 to 45.875/mm2
with increase of initial (Fe2O3) from 3% to 15%. The
significant change of the inclusion composition was not
observed during the experiment process for all the
slags.
Declaration of Competing Interest
The authors declare no conflicts of interest.
references
[1] Sankaranarayanan R, Guthrie R. Slag entraining vortexing
funnel formation during ladle teeming: similarity criteria
and scale-up relationships. Ironmak & Steelmak
2002;29:147e53.
[2] Mattias EK. Know the unknown: how carry-over slag varies
and how it impacts on the processing and product quality in
metals production. Stockholm: Metsol AB; 2013.
[3] Fruehan RJ, Misra S. ‘‘Hydrogen and nitrogen control in ladle
and casting operations,’’ AISI/DOE technology
RoadmapProgram report. Pittsburgh, PA: Carnegie Mellon
University; 2005.
[4] Steneholm K, Andersson N, Tilliander A, Jo € nsson PG. The role
of process control on the steel cleanliness. Ironmak Steelmak
2018;45:114e24.
[5] Doostmohammadi H, Andersson M, Steneholm K, Jonsson P.
Effect of EAF slag carryover on slag-metal equilibrium
calculations for ladle degassing process. TMS annual
meeting and exhibition. San Francisco: TMS; 2009.
[6] Mazumdar D, Singh OP, Dutta J. Reduction of tundish skull
and yield improvement in steel plants through physical
modeling of steelmaking tundish systems. Trans Indian Inst
Met 2011;64:593e605.
[7] Biswas J, Gnigdha S, Ballal NB, Basu S. A dynamic mixed-
control model for BOF metal-slag-gas reactions. Metall Mater
Trans B 2021;52:1309e21.
[8] Purchase W. Patent No. US 6602069 B2. Goricon
MetallurgicalServices Limited; 2003.
[9] Yu H, Yang D, Li M. Effects of Al addition on the reaction
between high manganese steel and CaO-SiO2-Al2O3-MgO
slag. Steel Res Int 2020;91:1e6. 2000143.
[10] Kim M, Lee SW, Cho JW, Park MS, Lee H-G, Kang YB. A
reaction between high Mn-high Al steel and CaO-SiO2-type
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 1 9 6 4 e1 9 7 5
molten mold flux: Part I. Composition evolution in molten
mold flux. Metall Mater Trans B 2013;44:299e308.
[11] Kang YB, Kim M-S, Lee S-W, Cho J-W, Park M-S, Lee H-G. A
reaction between high Mn-high Al steel and CaO-SiO2-type
molten mold flux: Part II. Reaction mechanism, interface
morphology, and Al2O3 accumulation in molten mold flux.
Metall MaterTrans B 2013;44:309e16.
[12] Sun H, Katsumi M. Oxidation rate of aluminum in molten
iron by CaO-SiO2-Al2O3-FeO-MnO slag. ISIJ Int
1996;36(Suppl):S34e7.
[13] Spooner S, Li Z, Sridhar S. Hidden phenomena during
transient reaction trajectories in liquid metals processing.
Metall Mater Trans B 2020;51:1301e14.
[14] Kim M, Park M, Jung S, Kim S, Kang Y. Reaction between high
Mn-high Al steel and CaO-SiO2-type molten mold flux:
retardation of Al2O3 accumulation at high Al content ([pct
Al]05) in steel and low MgO content (pct MgO0 1.8) in flux.
Metall Mater Trans B 2020;51:3067e78.
[15] Deo B, Boom R. Fundamentals of steelmaking metallurgy.
Hertfordshire, U.K.: Prentice Hall International; 1993.
[16] Rhamdhani MA, Coley KS, Brooks GA. Kinetics of metal/slag
reactions during spontaneous emulsification. Metall Mater
Trans B 2005;36:219e27.
[17] Cho Y, Cha W, Kang Y. Reoxidation of Al-killed ultra-low C
steel by FetO in RH slag: experiment, reaction rate model
development, and mechanism analysis. Metall Mater Trans B
2021;52:3032e44.
1975
[18] Robison JW, Pehlke RD. Kinetics of chromium oxide
reduction from a basic steelmaking slag by silicon dissolved
in liquid iron. Metall Mater Trans B 1974;5:1041e51.
[19] Kang YB. Progress of thermodynamic modeling for sulfide
dissolution in molten oxide slags: sulfide capacity and phase
diagram. Metall Mater Trans B 2021;52:2859e82.
[20] Bublik S, Bao S, Tangstad M, Einarsrud K. Interfacial
behaviour in Ferroalloys: the influence of sulfur in FeMn and
SiMn systems. Metall Mater Trans B 2021;52:3624e45.
[21] Webler BA, Pistorius PC. A review of steel processing
considerations for oxide cleanliness. Metall Mater Trans B
2020;51:2437e52.
[22] Todoroki H, Mizuno K. Effect of silica in slag on inclusion
compositions in 304 stainless steel: deoxidized with
aluminum. ISIJ Int 2004;44(8):1350e7.
[23] Yang S, Wang Q, Zhang L. Formation and modification of
MgO$Al2O3-based inclusions in alloy steels. Metall Mater
Trans B 2012;43:731e50.
[24] Wang L, Zhu H, Zhao J, Song M, Xue Z. Steel/refractory/slag
interfacial reaction and its effect on inclusions in high-Mn
high-Al steel. Ceram Int 2021;48:1090e7.
[25] Harada A, Matsui A, Nabeshima S. Effect of slag composition
on MgO$Al2O3 spinel-type inclusions in molten steel. ISIJ Int
2017;57:1546e52.
[26] Chen G, He S, Wang Q. Dissolution behavior of Al2O3 into
tundish slag for high- Al steel. J Mater Res Technol
2020;9:11311e8.