Effect of the CaO-Al2O3-Based Top Slag on the Cleanliness

of Stainless Steel During Secondary Metallurgy

PENGCHENG YAN, SHUIGEN HUANG, LIEVEN PANDELAERS, JORIS VAN DYCK,
MUXING GUO, and BART BLANPAIN

The ladle treatment of a 18 pct Cr-9 pct Ni stainless steel, with desulfurization as its main
purpose, was simulated on a laboratory scale. The influence of the top slag chemistry on the
steel cleanliness was evaluated. A higher steel cleanliness was obtained with an optimized lime-
alumina-based slag than with a lime-fluorspar-based slag. The inclusions were found to be
mainly in the form of oxysulfide; the alumina content in the inclusions first increased and
subsequently showed a slow drop, while the sulfide content decreased during the treatment. The
equilibrium between steel and inclusions was found to be more easily reached than that between
slag and steel. A slag–steel kinetic model was used to predict the steel chemistry evolution during
the treatment. Furthermore, a slag–steel–inclusions interaction kinetic model was developed to
calculate the change of alumina content in the inclusions during the ladle treatment. The sulfide
content of inclusions was also calculated and compared with the measured values.

DOI: 10.1007/s11663-013-9898-5
 The Minerals, Metals & Materials Society and ASM International 2013

I. INTRODUCTION removal[5,6]; and (2) CaO to absorb Al2O3 inclusions.[7,8]

STAINLESS steel products, due to their high corro-
sion resistance, have been widely used in areas ranging
from the process, to construction and transport indus-
tries. However, the product performance can be signif-
icantly affected by the steel cleanliness, e.g., the
nonmetallic inclusion number density, size distribution,
morphology and chemistry. For instance, lowering the
inclusion number density and size can extend the
bearing and fatigue life of steel products.[1,2] The
inclusion chemistry has a more complex impact. Oxide
inclusions, such as Al2O3, SiO2, and TiO2, can cause
cracking, while coating a layer of sulfide (MnS) on these
oxides may reduce their detrimental effect.[2–4] On the
other hand, the sulfide can also act as the starting point
of pitting corrosion and weaken the corrosion resistance
of stainless steel.[2–4] Top slag, because of its consider-
able effect on deoxidation and desulfurization, influ-
ences the inclusion chemistry during the secondary
metallurgy.[5,6] Meanwhile, the top slag can also reduce
the inclusion number density and area fraction through
the slag absorption effect.[7] Therefore, it is of significant
importance to investigate the influence of top slag on
steel cleanliness.
CaO-CaF2 (CSF)-based slag is commonly used in
stainless steel production. This slag has a good ability of
desulfurization/inclusion removal due to its high basi-
city, which allows enough (1) free oxygen ion for sulfur
PENGCHENG YAN, Ph.D. Student, SHUIGEN HUANG and
LIEVEN PANDELAERS, Academic Staff, JORIS VAN DYCK,
Technician, MUXING GUO and BART BLANPAIN, Professors, are
with the Department of Metallurgy and Materials Engineering
(MTM), KU Leuven, Kasteelpark Arenberg 44, Bus 2450, 3001
Leuven, Belgium. Contact e-mail: muxing.guo@mtm.kuleuven.be
Manuscript submitted February 21, 2013.
However, the CSF slag is so basic that C2S is formed
during the cooling of post-metallurgical process. The
phase transformation of b-C2S to c-C2S leads to slag
disintegration and consequently limits the slag valori-
zation potential.[9] In addition, leaching of fluorine-
containing compounds is also considered to be a
potential environmental issue. On the other hand,
CaO-Al2O3 (CA)-based slag (about 50 to 55 pct CaO,
40 to 45 pct Al2O3, £5 pct SiO2, and <1 pct FeO) has a
low oxidation potential, a low melting temperature
[ranges from 1623 K to 1723 K (1350 C to 1450 C),
and reaches a minimum at 42 to 48 pct Al2O3], and a
low viscosity [0.16 to 0.36 Pa s at temperatures between
1873 K and 1973 K (1600 C and 1700 C)].[10] From
both thermodynamic and kinetic points of view, this
CaO-Al2O3-based slag has excellent refining properties,
and therefore has been considered as a potential
substitute for the CaO-CaF2-based slag.
Against this background, the effect of top slag on the
steel cleanliness has been investigated by several
researchers. Yoon et al.[8] found that (1) increasing the
basicity of top slag did not affect the cleanliness of
bearing steel when the basicity (the CaO/SiO2 ratio) is
larger than 4, and (2) the adjustment of the CaO/Al2O3
ratio is the most effective way to remove inclusions—the
optimized CaO/Al2O3 ratio is around 1.7. Therefore,
those authors stressed that decreasing the melting
temperature through adjustment of the CaO/Al2O3 ratio
is more efficient than by controlling the slag composition
to reach the CaO-saturated region. Park et al.[11,12]
experimentally studied the effect of CaO-Al2O3-MgO
slag on the formation of Al2O3-MgO spinel inclusions in
ferritic stainless steel, and found that the inclusion
composition was relatively close to the slag composition,
i.e., the MgO-rich spinel solid inclusions were formed in
the steel melt, showing that a thermodynamic

METALLURGICAL AND MATERIALS TRANSACTIONS B

equilibrium was reached among slag, molten steel, and
inclusions. Choudhary et al.[13] have used a regular
solution model to calculate the activities of compounds,
e.g., Al2O3 and SiO2 in top slag, and successfully
predicted the formation of a spessartite-type inclusion
in FeMn/FeSi-killed steel. Björklund et al.[14] pointed
out that the top slag and the steel bulk are not in
equilibrium with respect to oxygen during ladle treat-
ment, whereas, by experimentally measuring the oxygen
activity both in slag (CaO-Al2O3-based) and steel bulk,
Coletti et al.[15] concluded that the slag is in a pseudo-
equilibrium with a limited amount of steel. These
studies,[11–14] however, were mainly focused on the
thermodynamic aspect of the slag–steel–inclusions inter-
action. Considerations on the kinetics, which is impor-
tant for production practice, are fairly limited.
Okuyama et al.[16] developed a kinetic model based on
two-film theory and predicted the evolution of MgAl2O4
inclusions by means of initial slag and steel chemistry;
they concluded that by reducing the CaO/SiO2 and
CaO/Al2O3 ratio of the top slag, the MgO content in
Al2O3-based inclusions can be decreased. However, the
influence of top slag on compositional evolution of
inclusions other than MgAl2O4 spinel has not been
investigated. Moreover, the stainless steel cleanliness
factors, e.g., nonmetallic inclusion number density, size
distribution, morphology, and chemistry, by means of
CaO-CaF2- and CaO-Al2O3-based slags, have not been
compared. Therefore, it is necessary to understand the
influence of CaO-Al2O3-based slag on stainless steel
cleanliness before its use in practice.
In the current article, the ladle treatment of a 18 pct
Cr-9 pct Ni stainless steel was simulated on a laboratory
scale. The steel cleanliness in terms of inclusion number
density, area fraction, size, and chemistry by means of
different types of slag was compared. The slag–steel–
inclusions interactions were discussed based on thermo-
dynamic and  kinetic considerations.
  The sulfide capacity
0 aðOÞ [17]
(C0S ¼ exp  DG RT  fðSÞ ) of the inclusions was
calculated, and subsequently the sulfur content of the
inclusions was predicted. A kinetic model was developed
based on the film theory with respect to the slag–steel
interaction to predict the compositional evolution of the
molten steel. Furthermore, a slag–steel–inclusions inter-
action kinetic model was developed to calculate the
Al2O3 content evolution in the inclusions during the
treatment. The current study contributes to the optimi-
zation of the top slag composition for the improvement
of the steel cleanliness and the desulfurization of
stainless steel refining.
II. EXPERIMENTAL
A. Materials
To simulate the ladle treatment process of stainless
steel production, austenitic stainless steel (grade 302)
was procured from a steel plant after the argon oxygen
decarburization (AOD) process and used in the labora-
tory experiment. Table I shows the chemical composi-
tion of the steel measured with inductively coupled
plasma-atomic emission spectroscopy (ICP-AES, Var-
ian Liberty series II instrument with an axial plasma
configuration). Four types of slags were used during the
tests (Table II, measured with X-ray fluorescence spec-
troscopy (XRF, Philips PW 2400)). Slag A, a mixture of
lime (containing 94.5 pct CaO, 1.5 pct SiO2, and 1.5 pct
MgO) and fluorspar (containing 90 pct CaF2, 2.5 pct
CaO, and 5 pct SiO2), is currently being used during
ladle treatment in the stainless steel plant. Slags B (low
basicity) and D (high basicity) are CaO-Al2O3-based
synthetic slags, which contain a small amount of SiO2,
Fe2O3, MgO, and TiO2 as additives. The synthetic slag is
treated with pre-melting, which enables a good homo-
geneity and a fast melting of the slag during ladle
treatment.[6] Slag C, a mixture of reagent grade oxides,
i.e., CaO, Al2O3, and SiO2, is used to investigate the
kinetic influence and to compare with synthetic slags.
Apart from the steel and slags, ferroalloys, i.e., FeSi,
FeMn, and FeS, and Al were also employed in the test.
The chemical composition of the alloying agent

Table I. The Chemical Composition of Austenitic Stainless Steel Used in the Test (Weight Percent)

C Mn P S Si Cr Ni Mo Cu Ti Co N Al B
0.03 1.2 0.03 0.0015 0.44 18.3 7.96 0.28 0.36 0.001 0.166 0.057 — 0.0006

Table II. The Chemical Composition of the Top Slag and Experimental Conditions

Chemical Composition (Weight Percent) Alloy Addition (g)

Test No. Slag Remarks CaO Al2O3 Fe2O3 SiO2 MgO TiO2 CaF2 B* Al FeSi FeS FeMn Ar (L/min)
1 A CSF 81.8 — — 2.1 1.3 — 14.8 39 0 75 8 12 0
2 B CA1s 40.0 45.5 2.5 6.0 1.0 4.0 — 0.8 3 0 8 12 0
3 C CA 55.0 40.0 — 5.0 — — — 1.2 3 0 8 12 0
4 0.5
5 D CA2s 50.0 40.4 2.1 4.3 0.6 1.7 — 1.1 3 0 8 12 0
B* (basicity) = CaO/(Al2O3 + SiO2).

METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table III. Chemical Composition of the Alloy Agent (Weight Percent) and T.O Content Measure with LECO (ppm)
Type of Ferroalloy Si Mn
FeSi 75 — —
FeS — —
FeMn — 85
Al — —
Fig. 1—Schematic of the experimental set-up.
measured using ICP-AES is given in Table III. The
impurities level of the alloy is represented in terms of
total oxygen (T.O) and measured by LECO combustion
analyzer (TC-436 DR).
B. Experimental Procedure
The treatments were performed in a vacuum induc-
tion furnace (Figure 1, 60-kW power supply and 4-kHz
frequency). A loading chamber, a sampling device, and a
measurement tool were fitted on the furnace lid to allow
for slag addition, sampling, oxygen activity, and tem-
perature measurements. More details on the experimen-
tal set-up are given in a previous study.[18] The
experimental procedure and conditions are shown in
Figure 2 and Table II, respectively. 15 Kg of austenitic
stainless steel ingot was melted under Ar atmosphere in
a magnesia crucible (ID of 150 mm, OD of 176 mm, and
height of 275 mm). The temperature of the molten steel
was controlled in the range from 1873 K to 1923 K
(1600 C to 1650 C), followed by the addition of 8 g
FeS alloy (to regulate S level to 150) and addition of
12 g FeMn alloy. Thereafter, the oxygen activity and the
temperature of the molten steel were together measured
using Celox oxygen sensor with type B thermocouple
(provided by Heraeus Electro-Nite) probes. Subse-
quently, a steel sample in conical shape (the upper
diameter is 20 mm, lower diameter is 10 mm, and the
height is from 16 to 25 mm) was taken by dipping the
spoon sampler into the liquid bath (around 80 mm
below the liquid steel surface)[6] and rapidly withdrawing
METALLURGICAL AND MATERIALS TRANSACTIONS B
S Al Fe T.O
1.5 23 458
38 — 62 —
— — 15 360
— 100 — —
it, followed by quenching in air. The sampling was made
in the center of the crucible, where slag did not cover the
surface of liquid steel. Then, 150 g of slag was added to
the molten steel through the loading chamber, mean-
while 75 g FeSi alloy was added in tests 1; 3 g Al was
added in tests 2 through 5; and bottom Ar blowing was
introduced in test 4. After the designated time, another
steel sample was taken and quenched; immediately
another slag (150 g without alloy) addition was made.
The same procedures for steel sampling and slag
addition were followed, and slags were added in four
steps, and in total, five steel samples were taken. At the
end of the treatment, oxygen activity and temperature of
the molten steel were measured, and then the melt was
poured into a mold. An additional slag sample was
collected after the mold was cooled down.
C. Compositional Analysis and Inclusion
Characterization
The central part of the obtained steel sample was cut into
three parts. The first part of the steel sample was used for
total sulfur (T.S) and oxygen content measurement. The
detailed analysis method for T.S in steel and that for slag
composition has been already explained elsewhere.[18] The
T.O in steel sample was measured using a LECO. The
second part of the steel sample was prepared for microscopic
investigation. Characterization of the inclusion population
(size and composition) was conducted with a high-resolu-
tion scanning electron microscope (SEM XL-40 LaB6). The
SEM was equipped with an EDAX energy-dispersive
spectrometer (EDS) detector and Noran system, i.e., Seven
X-ray Microanalysis System (NSS). The latter can be used
to conduct automatic inclusion analysis (AIA). The max-
imum working magnification was set to 1000, and the
effective minimum detectable inclusion area was about
0.5 lm2, and at least 100 inclusions and 1 mm2 of steel
matrix were analyzed. The EDS information of the steel
matrix was first collected and set as background during the
analysis. In this way, the influence of the matrix on inclusion
chemistry can be reduced. The elemental distribution in
inclusions was analyzed using a field emission-electron
probe microanalysis (FE-EPMA JXA-8530F). The third
part of the steel samples was used for steel composition
determination and inclusion morphology characterization
by means of the inclusion extraction technique.[19] Around
0.3 g steel sample was dissolved in HCl acid solution (1:1) at
353 K (80 C), the nondissolvable inclusions were collected
on a membrane filter (0.25 lm) and subjected for SEM
observation; the solution is prepared for composition
measurement by inductively coupled plasma-atomic emis-
sion spectroscopy (ICP-AES)
Fig. 2—Schematic of the experimental procedure.

Table IV. The Inclusion Number Density, Size, and Area Fraction, the T.O and Sulfur in Steel Sample, as well as the Oxygen
Activity and Temperature of the Molten Steel, Where F.A Represents the Inclusion Area Fraction; a[O] the Oxygen Activity; T.O
and T.S: the Total Oxygen and Sulfur Content, Respectively

Inclusion Size (lm)

Time after Inclusion Inclusion
Sample First Slag Min. Max. Ave. No. density F.A T.O T.S a[O] Temp.
No. Addition (min) Dia. Dia. Dia. (/mm2) (Percent) (ppm) (ppm) (ppm) [K (C)]
T1-1 0 0.81 2.92 1.25 349 0.043 159 105 21 1872 (1599)
T1-2 24 0.81 3.08 1.20 96 0.011 83 35 — —
T1-3 42 0.81 3.02 1.35 94 0.014 85 14 — —
T1-4 51 0.81 2.17 1.23 187 0.022 94 14 — —
T1-5 60 0.81 2.67 1.20 122 0.013 86 15 17.1 1880 (1607)
T2-1 0 0.81 2.43 1.46 288 0.048 188 157 27 1874 (1601)
T2-2 14 0.81 2.45 1.57 373 0.073 236 148 — —
T2-3 24 0.81 3.49 1.46 368 0.063 115 136 — —
T2-4 40 0.81 1.78 1.15 337 0.035 63 117 — —
T2-5 60 0.81 2.92 1.48 290 0.050 110 110 20.7 1899 (1626)
T3-1 0 0.81 4.01 1.68 304 0.068 196 138 18 1925 (1652)
T3-2 10 0.81 4.11 1.28 269 0.034 79 100 — —
T3-3 21 0.81 2.85 1.43 151 0.024 97 60 — —
T3-4 34 0.81 3.25 1.10 156 0.015 182 43 — —
T3-5 49 0.81 2.58 1.44 201 0.032 240 29 23.8 1863 (1590)
T4-1 0 0.81 2.08 1.35 596 0.086 220 169 22 1870 (1597)
T4-2 12 0.81 2.77 1.48 640 0.110 287 119 — —
T4-3 27 0.81 2.35 1.48 458 0.078 186 105 — —
T4-4 42 0.81 2.34 1.17 191 0.021 97 84 — —
T4-5 57 0.81 1.91 1.05 77 0.006 79 62 22.5 1932 (1659)
T5-1 0 0.81 2.02 1.21 343 0.040 177 232 25 1874 (1601)
T5-2 10 0.81 3.05 1.19 180 0.020 158 230 — —
T5-3 20 0.81 2.52 1.18 76 0.009 66 85 — —
T5-4 35 0.81 2.70 1.28 68 0.009 55 59 — —
T5-5 50 0.81 2.33 1.03 74 0.006 45 37 19.0 1952 (1679)

III. EXPERIMENTAL RESULTS
A. Inclusion Population
The characterization results of inclusions, the T.O and
T.S contents in the steel samples, as well as the oxygen
activity (a[O]), and experimental temperature during the
treatment are summarized in Table IV. The inclusion
size is estimated as the diameter of a circle with the same
area of measured inclusion area; the inclusion number
density is the ratio of the observed inclusion number to
measured area of steel matrix; the inclusion area fraction
is the ratio of the observed area of inclusions to the
measured area of steel matrix.
The upper part of Figure 3 shows the size evolution of
the inclusion population after the first slag addition.
There is no considerable change in the average inclusion
size in tests 1 to 3; while the average inclusion size of
final samples are smaller in tests 4 and 5 (Table IV). The
lower part of Figure 3 shows the evolution of the inclu-
sion area fraction with the treatment time. The inclusion
area fraction decreases during the treatment in all the
tests, indicating that inclusion flotation and absorption
occurred with all types of the top slag. Moreover, the
lowest inclusion area fraction is observed in the final
steel sample of tests 4 and 5. Both the absence of large
inclusions and the relatively lower inclusion area frac-
tion in tests 4 and 5 imply that (1) bottom Ar blowing
significantly enhances inclusion removal from the mol-
ten steel; and (2) Type D slag, the lime-alumina-based
synthetic slag, exhibits improved inclusion absorption.
This is probably because the slag D is compositionally
more stable and is saturated with CaO during the
treatment,[18] suggesting a higher inclusion absorption
ability.[7,10]

METALLURGICAL AND MATERIALS TRANSACTIONS B


Fig. 3—The evolution of average inclusion size and area fraction
(F.A) during treatment, where the error bar indicates the largest and
smallest inclusions found in the steel sample.
The inclusion size distribution of the final steel
samples is shown in Figure 4. The population density
functions (PDFs) are obtained by dividing the frequency
of inclusions in a given bin (inclusion number per area)
with the bin width. In this way, the arbitrariness caused
by the choice of the number and size of the bins is
eliminated. Moreover, the PDF can provide a deeper
and more quantitative comprehension of the physical
process.[20] The fitted curves in Figure 4 are approxi-
mately quadratic, showing that the size distribution can
be represented with a log-normal probability density
function. The statistical distribution and properties for
the fitted PDF are listed in Table V.
The comparison of the density functions in Figure 4
shows that (1) a relatively lower inclusion population
density is obtained in tests 1 and 5, suggesting an
improved inclusion absorption with type A and D slag;
(2) with the same slag (type C in tests 3 and 4), a lower
inclusion population density (especially for large inclu-
sions, >1.0 lm) is observed in the test with Ar blowing
(test 4) than that without it (test 3). Moreover, the
statistical properties (Table V) show that the average
size of the inclusions is much smaller in test 4 than in test
3, substantiating an effective removal of large inclusions
with bottom Ar blowing.
B. Inclusion composition
Figure 5 depicts a typical evolution of the inclusions
during the treatment in test 5. It shows that (1) the
SiO2-Cr2O3-MnO complex inclusions are already pres-
ent in the steel before the start of the experiment. These
inclusions consist mainly of spherical and angular
shapes (Figure 5(a)). Apparently, this is the result of a
reduction (and/or alloying) operation at the end of
AOD process, where FeSi (and/or other alloys) is added
to recover Cr from high chromium oxides-containing
slag; (2) Al2O3 inclusions with plate-like and octahedral
shapes are formed because of FeSi/Al addition in the
treatment (Figures 5(b) and 5(c)); meanwhile, certain
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 4—Inclusion size distribution determined by the SEM–AIA
technique for the final steel samples (data points) and corresponding
probability density function-fitted lines.
amounts of Al2O3-SiO2-MnO-Cr2O3 inclusions with
spherical shape still exist in the steel sample; and (3) at
the end of the treatment, high Al2O3 content inclusions
with plate-like shape appeared (Figure 5(d)). This com-
positional and morphologic evolution is considered to
be the result of the slag–steel–inclusions interaction.
For each steel sample, at least 100 inclusions were
measured with the SEM-AIA, and the average compo-
sition was then obtained. Since the oxygen content in the
oxysulfide inclusions is not directly measured using
EDS, it is assumed that all measured Si, Al, and Cr are
in the form of SiO2, Al2O3, and Cr2O3, respectively. All
S in the oxysulfide inclusions is assumed to form MnS
first. The remaining Mn content after the formation of
MnS is considered to be in the form of MnO. Table VI
shows the analyzed compositions of inclusions and steel
samples (analyzed with the ICP-AES), in which the
symbol [ ] denotes a dissolved element in molten steel,
and L is the aluminum distribution between inclusions
and molten steel. It should be mentioned that the
variability of L arose from the compositional evolution
of both inclusions and liquid steel during the treatment.
Figure 6 gives an overview of inclusions found in steel
samples, and Figure 7 illustrates the compositional
evolution of the inclusions during the treatment after
slag addition.
The SEM–AIA analysis results (Figure 7 and
Table VI) indicate that (1) the inclusions before the
ladle treatment (i.e., before the top slag and alloy
addition) are in the form of SiO2-Cr2O3-Mn(O,S). As
mentioned previously, these inclusions are the result of
the reduction (and/or alloying) operation at the end of
the AOD process; (2) after FeSi (containing Al) and/or
the Al addition, the Al2O3 content of the inclusions
increases rapidly (specifically for the tests 3 and 5 with 3
g Al additions) at the early stage and then levels off (or
has a small drop). Meanwhile, other inclusion contents,
i.e., Cr2O3, SiO2, and MnO, decrease first and level off
(or increase slowly) afterward. The opposite changes in
content of Al2O3 against other oxides in Figure 7
suggests that the steel–inclusions interaction reaction
took place during the treatment as described in Eq. [1]
 Table V. Statistical Distribution and Properties Estimated from the Probability Density Function

Statistical Properties

Sample No. Slag Remark Type Mean (lm) Median (lm) Mode (lm) Standard Deviation
T1-5 CSF oxides 0.47 0.37 0.23 0.36
T2-5 CA1 synthetic 1.22 1.03 0.73 0.78
T3-5 CA oxides Log-normal 1.36 1.28 1.14 0.48
T4-5 CA oxides 0.71 0.66 0.56 0.29
T5-5 CA2 synthetic 0.85 0.82 0.76 0.24

Fig. 5—The typical evolution of inclusions during the treatment (test 5 as an example): (a) before the slag and ferroalloy addition; (b) and (c)
during the treatment; and (d) at the end of the treatment.

increase in Al2O3 content; (3)at the end of the experiment,

½Al] þ SiO2 ðor MnO, Cr2 O3 Þ ! Al2 O3
þ ½Si ðor Cr, Mn)]
½S] þ ðO2 Þ ¼ ðS2 Þ þ ½O]
that the dissolved Al in steel reduces the reducible
component of the inclusions, leading to a considerable
inclusions contain mainly Al2O3-SiO2-MnO-Cr2O3 with
ð1Þ low MnS contents (except for test 2). According to
thermodynamic calculations, these inclusions would be
saturated with corundum (Al2O3 and Cr2O3) at the
½2 experimental temperature; (4) as can be seen in Table VI
and Figure 7, there is a high MnS content in the
inclusions for test 2, while for other tests the MnS
content decreases with treatment time, and only a limited

METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table VI. Chemical Compositions of the Inclusions and Steel in the Different Samples (Weight Percent)

Steel Composition Inclusion

Sample No. Time (min) [Al] [Si] [Mn] [Cr] Al2O3 SiO2 MnO Cr2O3 MnS TiO2 L = (Al)/[Al]
T1-1 0 0 0.30 0.42 18.0 0.2 42.9 20.6 25.6 10.8 0 —
T1-2 24 0.002 0.33 0.42 18.1 35.3 31.9 18.1 13.6 1.1 0 9347
T1-3 42 0.003 0.47 0.44 18.0 48.2 20.9 16.2 14.7 0 0 8509
T1-4 51 0.002 0.75 0.48 17.9 33.5 29.8 21.5 14.8 0.4 0 8871
T1-5 60 0.002 0.75 0.48 17.9 32.0 34.3 25.1 8.6 0 0 8459
T2-1 0 0 0.30 0.80 18.0 0 28.8 42.5 18.4 10.2 0 —
T2-2 14 0.003 0.29 0.92 18.3 0 33.8 45.4 19.4 1.4 0 —
T2-3 24 0.004 0.44 0.82 18.2 5.7 26.3 15.9 21.7 30.3 0 760
T2-4 40 0.003 0.45 0.86 18.2 47.3 4.0 10.9 15.8 22.1 0 8342
T2-5 60 0.002 0.45 0.86 18.3 18.5 10.8 19.4 21.2 30.0 0 4893
T3-1 0 0 0.30 0.41 18.1 0.7 39.5 15.2 32.1 12.5 0 —
T3-2 10 0.006 0.56 0.44 18.2 68.6 7.9 1.8 15.1 6.6 0 6053
T3-3 21 0.004 0.51 0.43 18.2 73.3 9.1 6.1 10.7 0.8 0 9702
T3-4 34 0.004 0.45 0.48 18.2 58.1 14.2 15.9 9.9 1.9 0 7694
T3-5 49 0.003 0.41 0.45 18.2 58.7 15.0 16.3 9.3 0.7 0 10366
T4-1 0 0 0.30 0.42 18.0 0 33.3 29.5 25.4 11.8 0 —
T4-2 12 0.003 0.41 0.57 18.1 9.3 18.8 41.8 19.8 10.2 0 1647
T4-3 27 0.003 0.35 0.58 18.1 29.8 12.8 29.2 19.2 9.0 0 5253
T4-4 42 0.002 0.31 0.60 18.1 34.4 11.9 24.6 21.6 7.5 0 9096
T4-5 57 0.002 0.27 0.59 18.2 34.4 17.1 25.4 17.6 5.5 0 9101
T5-1 0 0 0.28 0.41 18.4 0.8 28.4 19.0 20.8 31.1 0 —
T5-2 10 0.008 0.55 0.51 18.0 54.3 13.2 12.3 11.3 2.9 5.9 3593
T5-3 20 0.007 0.56 0.57 18.1 91.4 0 0 4.3 4.5 1.4 6913
T5-4 35 0.007 0.52 0.56 18.1 86.2 0 0 8.4 5.2 1.9 6516
T5-5 50 0.005 0.48 0.54 18.2 79.9 0 0 5.4 4.2 11.1 8463

amount of the MnS remains in the inclusions in the final
steel samples. This is probably linked with the desulfur-
ization behavior (Reaction [2]) in the experiments, i.e., an
insufficient desulfurization[18] (e.g., test 2) leads to the
formation of sulfide inclusions in the steel; (5) slag
chemistry and alloy additions considerably influence the
compositional evolution of inclusions during the treat-
ment. A high content of Al2O3 has been observed in the
tests (tests 3 and 5) with 3 g Al additions, while a high
content of MnS is detected in the test 2 with low sulfide
capacity slag B.[18] TiO2-containing inclusions were
observed in test 5 with slag D containing TiO2—this is
probably due to the slag–steel reaction during the
treatment; (6) the comparison of Figures 7(c) and (d)
shows the effect of kinetic conditions on the inclusion
composition, i.e., bottom Ar blowing (Figure 7(d), test 4)
results in Al2O3 cluster formation and its flotation, and
therefore less Al2O3 content was observed in test 4[21]; (7)
comparing with the tests with CA-based slags (Test 2, 3,
5), a relatively lower Al2O3 content in inclusions was
obtained in test 1 with CSF slag. This is because (1) less
Al was induced in Test 1 through FeSi addition, and (2)
slag with high CaO and low Al2O3 contents shows a
strong and quick Al2O3 inclusions absorption behav-
ior.[10,22]
IV. THERMODYNAMIC AND KINETIC
CONSIDERATIONS
It is known that slag chemistry has considerable
impact on the [O] and [S] contents in steel through
desulfurization and deoxidation reactions. On the other
hand, oxides and/or sulfide inclusions also react with the
dissolved [O] and [S], resulting in changes of inclusion
composition during the experiments. Thus, the interac-
tions among the slag, steel, and inclusions should be
taken into account to describe the inclusion formation
and their compositional evolution.
A. Slag–Steel Interaction
1. Thermodynamic considerations
Top slag interacts with molten steel during the
secondary refining process, and further influences the
steel chemistry. In the present tests, the deoxidants Al
and Si (through FeSi alloy) as well as the top slag were
added to molten steel for ladle refining; thus, the
deoxidation reactions with respect to Al and Si are
mainly considered for slag–steel interactions. These
interactions can be expressed as follows[11,12]:
45300
2½Al] þ 3½O] ¼ ðAl2 O3 Þ; log K3 ¼  11:62 ½3
T
24600
½Si þ 2½O ¼ ðSiO2 Þ; log K4 ¼  8:4 ½4
T
where Ki is the equilibrium constant of (i). (Al2O3) and
(SiO2) are the Al2O3 and SiO2 contents in the slag, respec-
tively. According to Eqs. [3] and [4], the activities of [Al]
and [Si] in molten steel after equilibration with top slag
can be calculated based on [O] activity in molten steel,
and the activities of Al2O3 and SiO2 in slag, and here the

METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 6—The overview of inclusions found in steel samples.
obtained activities of [Al] and [Si] are denoted as ‘‘calcu-
lated’’ values. In the calculation, the measured a[O] and
temperature values at the end of the tests (Table IV) are
used; and the activities of Al2O3 and SiO2 in the final slag
are estimated using two approaches. The first one is by
using final slag chemistry (Table VII, measured with
XRF) with the aid of the FactSage software. The slag
equilibrium was calculated with the equilibrium module
at the experimental temperature, and the activities of
Al2O3 and SiO2 in liquid slagA were then obtained. The
FToxide and FACT53 database are employed during the
estimation, and hereafter these results will be denoted as
‘‘equilibrated with top slag.’’ The second approach is to
assume that the slag has saturated with Al2O3 and SiO2,
i.e., activities of the oxides (i.e., Al2O3 and SiO2) are unity
and is indicated with ‘‘unity.’’ On the other hand, the
activities of [Al] and [Si] can be obtained from Eqs. [5]
and [6][23] using compositional analysis results of the steel
samples (Table VI) and interaction parameters
(Table VIII), and is denoted as ‘‘measured’’ values. The
second-order parameters are not used in the calculation
because of lack of data and their limited influence on cal-
culation results.
a½j ¼ f½j ½pctj ½5
X must be Al2O3 and SiO2 concentration gradients from
log f½j ¼ eij ½pcti ½6
where j represents the dissolved elements in molten steel;
a[j] the activity of dissolved element j; f[j] the activity
coefficient of j; eij the interaction parameter of i for j
element; [pct i] and [pct j] are the weight percentage of i
and j in the molten steel, respectively.
A comparison of the measured activities (a[Al] and
a[Si]) with the calculated values is given in Figure 8. The
calculated activities are assumed to be equilibrated with
the top slag and pure oxide, i.e., Al2O3 and/or SiO2,
respectively. It is clear that the measured values (a[Al]
and a[Si]) are larger than the calculated values when steel
is assumed to be equilibrated with the top slag (see the
open squares and circles in Figure 8), while the mea-
sured values are lower than the calculations with the
oxide-saturated slag (see the solid squares and circles in
Figure 8), and it is more obvious for the Si deoxidation
reaction, i.e., Si activity in molten steel is far from the
equilibrium both with top slag and pure SiO2. This
indicates that (1) the slag–steel interaction did not reach
equilibrium during the treatment; and (2) the reactions
can proceed to increase the oxide (Al2O3 and SiO2)
content in the slag and cease before the slag is saturated
with them if a longer slag–steel interaction is allowed. In
general, it is believed that the reaction has reached
equilibrium at the slag/steel interface at high tempera-
ture, and this is corroborated by a number of laboratory
studies and industrial trials.[12,15,30] Therefore, there
the slag/steel interface toward the slag bulk. Actually,
these concentration gradients are considered to be both
the thermodynamic and kinetic driving forces for the
reactions. To evaluate the steel and slag interaction and
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 7—The compositional evolution of inclusions during the treatment.
its influence factors during the treatment, the slag–steel
interaction kinetics should be investigated.
2. Kinetic calculations
The slag–steel reaction kinetics can be described based
on a modified two-film theory[31] that the reducible
METALLURGICAL AND MATERIALS TRANSACTIONS B
compounds, e.g., FeO, are reduced by [Al] and/or [Si] at
the slag/steel interface (Reaction [7]). A schematic
representation of the interaction between the slag and
molten steel is illustrated in Figure 9. Since chemical
reactions at the slag/steel interface at steelmaking
temperatures are fast enough, the rate-limiting step in
 Table VII. Chemical Composition of the Final Slag (Weight Percent)

Test No. CaO SiO2 MgO Al2O3 Cr2O3 Fe2O3 MnO CaF2
1 51.0 17.2 8.2 8.0 0.9 1.0 0.6 13.0
2 43.7 5.0 2.8 44.8 0.9 1.6 0.4 —
3 51.6 8.8 4.1 36.0 — — — —
4 44.2 9.7 4.5 41.3 — — — —
5 50.9 6.6 3.8 38.6 — — — —

Table VIII. Interaction Parameters Used in Calculation

j Si Al Cr Mn O References
Si 0.103 0.058 — 0.033 0.119
Al 0.056 0.044 0.0096 0.035 34740/T+11.95 [24–29]
Mn — — 0.0042 — 0.083

Fig. 8—Comparison of the calculated a[Al] and a[Si] and the corre- Fig. 9—Schematic of the slag–steel interaction.
sponding measured values in molten steel, where FS and Unity mean
oxide activity in slag estimated using FactSage and assumed to be 1,
respectively.

this case is considered to be the mass transport. The
equation for mass transport can be expressed as
Eq. [8].
½Al(or Si)] + FeO ! Al2 O3 ðor SiO2 Þ + [Fe]
Ji ¼ ks ðCðiÞ  CðiÞ Þ ¼ km ðC½i  C½i Þ
where Ji is the flux of compound i, mol/(m2 s) through
the slag/steel interface; km and ks are the mass transfer
coefficient of i at the steel and slag side, respectively, m/
s; and C(i), CðiÞ , C[i], and C½i are the concentrations of i
in the slag, at the slag/steel interface in the slag, in the
steel and at the slag/steel interface in the steel, respec-
tively, mol/m3. According to Eq. [8], changes in the con-
centration of [i] in the molten steel during the treatment
can be expressed as Eq. [9] by assuming that the rate-
limiting step is the mass transport on the steel side:
d½i qm  A  km
 ¼ f½i  ½i g
dt Wm
or as Eq. [10] if the rate-limiting step is the mass trans-
port on the slag side:
d½i qs  A  ks
 ¼ fðiÞ  ðiÞ g ½10
½7 dt Wm
where A is the contact area of slag/steel interface, m2; t is
½8 the time after the slag/alloy addition, s; Wm is the weight
of molten steel, kg; (i), (i)*, [i], and [i]* and are,
respectively, the concentrations of i in the bulk of the
slag phase, at the slag/steel interface on the slag side, in
the bulk of the steel phase, and at the slag/steel interface
on the steel side, wt pct; and the qs and qm are,
respectively, the densities of slag and molten steel at the
experimental temperature, kg/m3;
The compositional evolution in molten steel was
computed from Eqs. [9] and [10]. Since the mass transfer
of [Si] in the steel phase cannot be accurately pre-
dicted—because of the different procedures for FeSi
addition, i.e., FeSi was only added in test 1, and because
½9 of the heterogeneity of the slag (dispersed Si-enriched
metal droplets),[12] we only focused on the calculation of

METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 10—The situation of the slag–steel contact during the treatment: (a) picture of the slag and steel in the crucible; (b) schematic diagram of
the slag–steel contact.
the [Al] evolution during the treatment. It should be
noted that the changes in [Al] during the treatment can
be caused by two aspects, i.e., (1) the [Al] increase due to
the addition of aluminum and FeSi, and (2) [Al]
decrease owing to the slag–steel interaction. Here, the
latter, i.e., [Al] oxidation by the reducible components in
slag is considered. According to the literature,[12,15,30]
the mass transfer of aluminum in molten steel is the rate-
limiting step, and the mass transfer coefficient of
2.0 9 104 m/s was used.[15,30] By integrating Eq. [9]
with respect to the slag–steel reaction time, the [Al]
evolution can be calculated from Eq. [11].
 
q m  A  km  t
½Al] ¼ exp  f½Al  ½Aleq g þ ½Al]eq
Wm
½11
where the equilibrated [Al]eq is used as the [Al] content
at the slag/steel interface. Since the slag covered only
around one fourth of the molten steel surface during the
experiment, the slag/steel interface area is considered to
be one fourth of the cross section of the crucible in the
calculation (Figure 10). The detailed parameters and
experimental conditions used in the calculations are
summarized in Table IX.
Figure 11 shows the calculated results of the [Al]
evolution in molten steel during the treatment together
with the experimental data. Except for test 5, the
calculations are in good agreement with the experimen-
tally measured values. This implies that (1) the assump-
tion of the present calculation is reasonable, in which the
[Al] oxidation takes place at the slag/steel interface
Table IX. The Parameters Used in the Calculation of Eq. [11]
Test No. Slag Remark A (m2)
1 CSF oxides
2 CA1 synthetic
3
3 CA oxides 4.4 9 10
4 CA oxides
5 CA2 synthetic
METALLURGICAL AND MATERIALS TRANSACTIONS B
(i.e., through the slag/steel permanent contact reaction)
and the mass transfer of [Al] in molten steel is
considered to be the rate-limiting step; (2) for a given
test, the [Al] oxidation rate (see the slope of the
calculated curves at different times) decreases with
decreasing aluminum content in the steel, implying a
decrease in the driving force of the reaction with the
reaction time; (3) the calculated curves show a further
decreasing tendency of [Al] content after around
60 minutes’ treatment, indicating that the slag–steel
interactions have not reached equilibrium, i.e., the [Al]
oxidation by the reducible component (e.g., FeO) in the
slag would have continued if a longer slag–steel inter-
action had been allowed. This again confirms the results
of the thermodynamic analysis in Figure 8. Although
there was a discrepancy in test 5, which is probably due
to an error of the [Al] measurement, the overall results in
Figure 11 on the prediction of the [Al] evolution during
the treatment suggest a promising application of the
present kinetic model.
B. Slag–Steel–Inclusions Interaction
1. Sulfur content of inclusions
As seen in Table VI, the inclusions observed in the
steel samples were in the form of oxysulfides. In general,
the S content of an inclusion is mainly influenced by the
sulfide capacity of the inclusion (C0S ) and the solidifica-
tion procedure.[32,33] Since C0S is only dependent on the
oxide composition of the inclusions and temperature,
the C0S of the observed SiO2-MnO-Cr2O3-Al2O3 inclu-
sions can be calculated by means of the analysis results
km (m/s) qm (kg/m3) [Al] (ppm) [Al]eq (ppm)
30 1
40 10
4
2.0 9 10 7000 60 10
30 11
80 17
of the inclusion chemistry and the experimental tem-
peratures. Furthermore, the equilibrated sulfur distri-
bution L0S (= (S)incl/[S], the ratio of sulfur content
between the inclusions and molten steel) can be calcu-
lated by considering inclusion composition, experimen-
tal temperature, and oxygen activity. The inclusion’s
composition and experimental temperature influence the
inclusion sulfide capacity, and the oxygen activity has
negative effect on L0S .[18,32] The detailed calculation
approach and discussion have been given in our
previous paper.[18] On the other hand, the measured
L0S can be obtained from the measured sulfur content of
both the inclusions and the steel. Figure 12 shows the
relationship between the sulfur distribution L0S and the
inclusion sulfide capacity C0S in logarithmic form.
The measured and calculated equilibrated L0S values
agree with each other in range of log C0S 3.0 to 2.0
(Figure 12). Therefore, the S content of the inclusion
(S)incl can be calculated once the inclusion sulfide
Fig. 11—Comparison of the measured and calculated values for the
evolution of [Al] content in molten steel during the treatment.
Fig. 12—Relation between the sulfur distribution L0S and the inclu-
sion sulfide capacity C0S , where the square and dot refer to equili-
brated and measured sulfur distribution between inclusions and steel,
respectively.
capacity C0S and sulfur content [S] in molten steel are
known. Because (1) the equilibrated L0S is directly linked
with inclusion sulfide capacity, and the latter can be
estimated based on the oxides chemistry and experi-
mental temperature; and (2) the sulfur content in molten
steel can be obtained from the top slag chemistry, initial
[S] content and experimental temperature,[18] the S
content in the complex inclusions can be practically
evaluated under steel–inclusion equilibrium conditions.
However, a considerable calculation error may result if
the inclusion-steel interaction is far away from the
equilibrium. As seen in Figure 12, the inclusions with
lower C0S value (log C0S < 3.0) were supersaturated
with sulfur, while that with higher C0S value (log
C0S > 2.0) were undersaturated with sulfur The former
is probably because the sulfur solubility in steel
decreases during the solidification, leading to further
precipitation of MnS on the inclusions even after their
having been saturated with sulfur. The latter may be
owing to the low sulfur content in steel, which makes the
sulfur transfer from steel to inclusions difficult.[18]
2. Deoxidation equilibrium between steel and inclusions
The deoxidation reactions to form complex oxide
inclusions can be described through Eqs. [12] to
[15].[12,29] Similar to the case of the slag–steel reactions,
the activities of Al2O3, SiO2, MnO, and Cr2O3 in the
inclusion complex can be calculated based on element
activities in molten steel. The obtained activities by such
approach are denoted as the ‘‘Equilibrated’’ value.
During the calculation, the activities of [Al], [Si], [Mn],
and [Cr] are obtained through Eqs. [5] and [6],[23] based
on the measured steel composition (Table VI), and the
measured oxygen activity is used. On the other hand, the
activities of Al2O3, SiO2, and MnO can be directly
estimated based on the average inclusion chemistry
(Table VI measured with SEM-AIA) with the aid of the
FactSage software, which is denoted as the ‘‘FactSage’’
value. In the FactSage estimation, the equilibrium
module is used at the experimental temperature and
the activities of SiO2 and MnO are obtained; the Al2O3
and Cr2O3 exist both in the slag and corundum phases,
and to simplify the estimation, their activities are set to
one. Figure 13 shows the comparison of the calculated
activities of Al2O3, SiO2, and MnO in inclusions with
the measured values.
45300
2½Al] þ 3½O] ¼ ðAl2 O3 Þincl ; log K9 ¼  11:62
T
½12
24600
½Si þ 2½O ¼ ðSiO2 Þincl ; log K10 ¼  8:4 ½13
T
11070
½Mn] þ ½O] ¼ ðMnO)incl ; log K11 ¼  4:53 ½14
T
36200
2½Cr] þ 3½O] ¼ ðCr2 O3 Þincl ; log K12 ¼  16:00
T
½15
METALLURGICAL AND MATERIALS TRANSACTIONS B
 It can be seen from Figure 13 that the Equilibrated
activity data deviate from the FactSage values if the log
a(MxOy) is higher than 1, and the discrepancy increases
with increasing oxide activity. This deviation implies
that there are large driving forces for the further steel–
inclusions reactions to lower the SiO2, Al2O3, and Cr2O3
activities. The large deviations for the Cr2O3 and Al2O3
activities at their saturated states (corundum existence)
are probably due to the slow steel–inclusions interac-
tion. In other words, the existence of solid corundum
limits the steel–inclusions reactions.
Based on the above experimental results (Figure 7
and Table VI) and discussions (Figures 8, 11, and 13) on
the slag–steel–inclusions interactions, we propose the
possible mechanisms of the reactions and changes in the
inclusion compositions during the ladle treatment as
follows: (1) After AOD refining, there were SiO2-Cr2O3-
Mn(O,S) inclusions in the steel before the ladle treat-
Fig. 13—Comparison of the calculated activities of Al2O3, SiO2, and
MnO in the inclusions with measured values.
Fig. 14—Inclusion transformation during treatment (measured with FE-EPMA).
METALLURGICAL AND MATERIALS TRANSACTIONS B
ment (i.e., before top slag and alloy addition); (2) After
the FeSi and Al additions in the ladle treatment, the
original SiO2-Cr2O3-Mn(O,S) type inclusions were
reduced with [Al] through the Reaction [1], resulting in
the Al2O3 content increase in inclusions; (3 ) The [Al],
meanwhile, also reacted with the reducible compounds
in the slag, decreasing the dissolved Al in the steel
(Figure 11 and Table VI); , (4) Then, the reduction
reaction of the SiO2-Cr2O3-Mn(O,S) inclusions by the
dissolved Al slowed down and finally ceased at a certain
[Al] concentration, where the reduction reaction (Reac-
tion [1]) had equilibrated (Figure 7 and Table VI); and
(5)With the further consumption of [Al] through the
slag–steel interaction, the dissolved Al in liquid steel
became so low that the newly formed Al2O3 in the
inclusions started to be reduced with [Mn], [Si], and [Cr],
resulting in a slow drop in the Al2O3 content (Figure 7
and Table VI). Further slag–steel–inclusions reaction
kinetics have been investigated in the next section to
better understand this proposed mechanism.
3. Slag–steel–inclusions interaction kinetics
On the basis of the above understanding with respect
to the compositional evolution of inclusions during the
treatment, a kinetic model is developed to interpret the
effect of slag–steel–inclusions interactions on inclusion
chemistry. Figure 14 is the compositional evolution of
the inclusions during the treatment (measured with FE-
EPMA), where A represents an original SiO2-Cr2O3-
Mn(O,S) inclusion before the ladle treatment; B a
modified inclusion after FeSi (containing Al) and/or
Al addition in the experiment through the Reaction [1],
i.e., the reduction reaction of the SiO2-Cr2O3-Mn(O, S)
inclusion by the dissolved Al; S a Al2O3-saturated
inclusion or pure Al2O3 (as long as [Al] is high enough,
the original SiO2-Cr2O3-Mn(O,S) inclusion can be
reduced into pure Al2O3); and F the final inclusion, in
which the oversaturated Al2O3 in inclusion has been
reduced with [Mn] and [Si] in the steel, resulting in an
Al2O3 content drop in the inclusion. The mass transfer Figure 15 shows the measured Al2O3 content in
inside the inclusion was assumed to be the rate-limiting inclusions with AIA and the calculated curves of
step in the following mathematical modeling because of Al2O3 content changes in inclusions as a function of
the existence of the solid corundum phase, which limits time after slag addition. A good agreement between the
the mass transfer in the reactions.[34,35] To simplify the calculated and measured data is obtained. Both the
mathematical model and calculation, the following calculated and the measured date show that the Al2O3
assumptions were made: content in the inclusions increases rapidly at the
beginning of the treatment, followed by a gradual
(1) The inclusion is spherical and the diameter of the
decrease. This quantitatively confirms the reliability of
inclusion does not change over time;
the present slag–steel–inclusions interaction model (i.e.,
(2) The inclusion density does not change during the
Figure 14 and Eq. [16]), in which the original type A
inclusion evolution;
(SiO2-Cr2O3-Mn(O,S)) inclusion is first reduced with
(3) The chemical reaction on the steel/inclusion inter-
[Al], being transformed into type B (Al2O3-SiO2-Cr2O3-
face is faster compared with the rate-limiting diffu-
Mn(O,S)) and into type S (Al2O3 saturated-SiO2-Cr2O3-
sion.
Mn(O,S)) if the [Al] content is high enough, and then
Since the SiO2 and MnO ratio of the inclusions hardly this Al2O3-saturated type S inclusion reacts with [Mn]
changed during the treatment, main attention in the and [Si] in the steel, resulting in a slow drop of Al2O3
modeling was paid on the changes of Al2O3 content in content, i.e., being transformed into type F inclusions.
the inclusions. The diffusion of aluminum can be On the other hand, the quick increase of Al2O3 content
expressed as follows: at the beginning, followed by a slow Al2O3 content drop
   (Figure 15) implies that the reaction between steel and
dðAlÞ 1 d 2 dðAlÞ inclusions (i.e., the type A inclusions reduced with [Al]
¼D 2 r ½16
dt r dr dr through the Reaction [1]) was much faster than that
between slag and steel, which oxidizes [Al] to a low
where D is the diffusion coefficient of aluminum ion in enough content by the reducible components in the slag,
alumina, m2/s; rincl is the radius of the inclusion, m; the resulting in transformation of inclusions from type S to
Eq. [16] is solved numerically using a finite volume F. This is attributed to the larger specific steel/inclusions
discretization[36] and following boundary conditions: interface than slag/steel interface. The good agreement
(1) (Al) = (Al), at t = 0 second and r < rincl; between the measured and the calculated Al2O3 content
(2) [Al]i=[Al], at t = 0 second and r = rincl; values suggests the possible application of this model to
(3) (Al)i =L[Al], at t > 0 and r = rincl; predict the compositional evolution of inclusions based
dðAlÞ on the slag and steel chemistry. In other words, to
(4) ¼ 0; at r ¼ 0;
dr
where L is the distribution ratio of aluminum between
the inclusion and steel (Table VI); (Al)i, (Al), [Al], and
[Al] are, respectively, the aluminum content at the
interface in the inclusion, in the inclusion at time = 0
second, and in the steel bulk before and after the steel–
inclusions interaction, wt pct.
By coupling the results of the slag–steel kinetic model
(Figure 11) with boundary condition (3), the slag–steel–
inclusions interaction can be quantitatively investigated.
For the calculation, the average aluminum distribution
(L) between inclusions and steel was estimated through
the compositional analysis (Table VI), and the value of
L = 8 9 103 was used. The diffusion coefficient of
aluminum in single crystal alumina is taken as
6.0 9 1017 m2/s at 1873 K (1600 C).[34] This value is
of the same magnitude as Al3+ diffusion in solid spinel
Fig. 15—Comparison of the measured and calculated values for
at 1873 K (1600 C).[35] The other calculation parame- Al2O3 content in inclusions as a function of time.
ters are illustrated in Table X.

Table X. The Parameters Used in the Calculations of Eq. [16]

Test No. Slag Remark L D (m2/s) Dia. (lm) (Al) (Percent) [Al] (ppm)
1 CSF oxides 1.24 25.2 30
2 CA1 synthetic 3 17
1.42 3.0 40
3 CA oxides 8 9 10 6.0 9 10 1.38 36.0 60
4 CA oxides 1.30 4.9 30
5 CA2 synthetic 1.18 28.7 80

METALLURGICAL AND MATERIALS TRANSACTIONS B

obtain the target inclusion’s composition in the final
product during the ladle treatment, the slag chemistry
can be optimized by means of this model.
V. CONCLUSIONS
Ladle treatment of 18 pct Cr-9 pct Ni stainless steel
after the AOD process was simulated on a laboratory
scale. The effects of slag chemistry on the steel and
inclusions’ compositions were discussed with thermody-
namic and kinetic considerations. The steel cleanliness in
terms of factors for different types of slag are compared.
The main results are as follows:
1. Improved steel cleanliness, i.e., in terms of lower
inclusion number density, area fraction, and smaller
inclusion size, was obtained with the optimized lime-
alumina-based slag, compared with the lime-fluor-
spar-based slag. The optimized lime-alumina-based
slag can be used during ladle refining of stainless steel
for controlling the steel cleanliness.
2. The inclusions were mainly in the form of oxysulfide.
The sulfur content of the inclusions decreased during
the treatment because of the effect of slag. The Al2O3
content in the steel increased immediately after the
slag and alloy addition, followed by a slow drop due
to the consumption of [Al] during the slag–steel
interactions.
3. The sulfide capacity of the inclusions was calculated
based on the measured inclusion chemistry, and
subsequently used to predict the sulfur content of the
inclusions
4. A slag–steel kinetic model based on film theory was
developed for the prediction of the compositional
evolution of molten steel. The calculated [Al] evolu-
tion during the treatment was in good agreement
with experimental data, suggesting a promising
application of the kinetic model.
5. A slag–steel–inclusions kinetic model was developed
to predict the evolution of the Al2O3 content in the
inclusions as a function of time, taking the mass
transfer in the inclusion as the rate-limiting step.
Good agreement was obtained with the experimental
results.
REFERENCES
1. R. Kiessling: Met. Sci., 1980, vol. 14, pp. 161–72.
2. M. Wakoh, T. Sawai, and S. Mizoguchi: ISIJ Int., 1996, vol. 36,
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