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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]


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

METALLURGICAL AND MATERIALS TRANSACTIONS B


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


FeSi 75 — — 1.5 23 458
FeS — — 38 — 62 —
FeMn — 85 — — 15 360
Al — — — 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


Fig. 1—Schematic of the experimental set-up. Characterization
The central part of the obtained steel sample was cut into
measured using ICP-AES is given in Table III. The three parts. The first part of the steel sample was used for
impurities level of the alloy is represented in terms of total sulfur (T.S) and oxygen content measurement. The
total oxygen (T.O) and measured by LECO combustion detailed analysis method for T.S in steel and that for slag
analyzer (TC-436 DR). composition has been already explained elsewhere.[18] The
T.O in steel sample was measured using a LECO. The
B. Experimental Procedure second part of the steel sample was prepared for microscopic
investigation. Characterization of the inclusion population
The treatments were performed in a vacuum induc- (size and composition) was conducted with a high-resolu-
tion furnace (Figure 1, 60-kW power supply and 4-kHz tion scanning electron microscope (SEM XL-40 LaB6). The
frequency). A loading chamber, a sampling device, and a SEM was equipped with an EDAX energy-dispersive
measurement tool were fitted on the furnace lid to allow spectrometer (EDS) detector and Noran system, i.e., Seven
for slag addition, sampling, oxygen activity, and tem- X-ray Microanalysis System (NSS). The latter can be used
perature measurements. More details on the experimen- to conduct automatic inclusion analysis (AIA). The max-
tal set-up are given in a previous study.[18] The imum working magnification was set to 1000, and the
experimental procedure and conditions are shown in effective minimum detectable inclusion area was about
Figure 2 and Table II, respectively. 15 Kg of austenitic 0.5 lm2, and at least 100 inclusions and 1 mm2 of steel
stainless steel ingot was melted under Ar atmosphere in matrix were analyzed. The EDS information of the steel
a magnesia crucible (ID of 150 mm, OD of 176 mm, and matrix was first collected and set as background during the
height of 275 mm). The temperature of the molten steel analysis. In this way, the influence of the matrix on inclusion
was controlled in the range from 1873 K to 1923 K chemistry can be reduced. The elemental distribution in
(1600 C to 1650 C), followed by the addition of 8 g inclusions was analyzed using a field emission-electron
FeS alloy (to regulate S level to 150) and addition of probe microanalysis (FE-EPMA JXA-8530F). The third
12 g FeMn alloy. Thereafter, the oxygen activity and the part of the steel samples was used for steel composition
temperature of the molten steel were together measured determination and inclusion morphology characterization
using Celox oxygen sensor with type B thermocouple by means of the inclusion extraction technique.[19] Around
(provided by Heraeus Electro-Nite) probes. Subse- 0.3 g steel sample was dissolved in HCl acid solution (1:1) at
quently, a steel sample in conical shape (the upper 353 K (80 C), the nondissolvable inclusions were collected
diameter is 20 mm, lower diameter is 10 mm, and the on a membrane filter (0.25 lm) and subjected for SEM
height is from 16 to 25 mm) was taken by dipping the observation; the solution is prepared for composition
spoon sampler into the liquid bath (around 80 mm measurement by inductively coupled plasma-atomic emis-
below the liquid steel surface)[6] and rapidly withdrawing sion spectroscopy (ICP-AES)

METALLURGICAL AND MATERIALS TRANSACTIONS B


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

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

METALLURGICAL AND MATERIALS TRANSACTIONS B


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 inclusions contain mainly Al2O3-SiO2-MnO-Cr2O3 with
þ ½Si ðor Cr, Mn)] ð1Þ low MnS contents (except for test 2). According to
thermodynamic calculations, these inclusions would be
saturated with corundum (Al2O3 and Cr2O3) at the
½S] þ ðO2 Þ ¼ ðS2 Þ þ ½O] ½2 experimental temperature; (4) as can be seen in Table VI
and Figure 7, there is a high MnS content in the
that the dissolved Al in steel reduces the reducible inclusions for test 2, while for other tests the MnS
component of the inclusions, leading to a considerable 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 desulfurization and deoxidation reactions. On the other
steel samples. This is probably linked with the desulfur- hand, oxides and/or sulfide inclusions also react with the
ization behavior (Reaction [2]) in the experiments, i.e., an dissolved [O] and [S], resulting in changes of inclusion
insufficient desulfurization[18] (e.g., test 2) leads to the composition during the experiments. Thus, the interac-
formation of sulfide inclusions in the steel; (5) slag tions among the slag, steel, and inclusions should be
chemistry and alloy additions considerably influence the taken into account to describe the inclusion formation
compositional evolution of inclusions during the treat- and their compositional evolution.
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 A. Slag–Steel Interaction
capacity slag B.[18] TiO2-containing inclusions were 1. Thermodynamic considerations
observed in test 5 with slag D containing TiO2—this is Top slag interacts with molten steel during the
probably due to the slag–steel reaction during the secondary refining process, and further influences the
treatment; (6) the comparison of Figures 7(c) and (d) steel chemistry. In the present tests, the deoxidants Al
shows the effect of kinetic conditions on the inclusion and Si (through FeSi alloy) as well as the top slag were
composition, i.e., bottom Ar blowing (Figure 7(d), test 4) added to molten steel for ladle refining; thus, the
results in Al2O3 cluster formation and its flotation, and deoxidation reactions with respect to Al and Si are
therefore less Al2O3 content was observed in test 4[21]; (7) mainly considered for slag–steel interactions. These
comparing with the tests with CA-based slags (Test 2, 3, interactions can be expressed as follows[11,12]:
5), a relatively lower Al2O3 content in inclusions was
obtained in test 1 with CSF slag. This is because (1) less 45300
2½Al] þ 3½O] ¼ ðAl2 O3 Þ; log K3 ¼  11:62 ½3
Al was induced in Test 1 through FeSi addition, and (2) T
slag with high CaO and low Al2O3 contents shows a
strong and quick Al2O3 inclusions absorption behav- 24600
ior.[10,22] ½Si þ 2½O ¼ ðSiO2 Þ; log K4 ¼  8:4 ½4
T
where Ki is the equilibrium constant of (i). (Al2O3) and
IV. THERMODYNAMIC AND KINETIC (SiO2) are the Al2O3 and SiO2 contents in the slag, respec-
CONSIDERATIONS tively. According to Eqs. [3] and [4], the activities of [Al]
and [Si] in molten steel after equilibration with top slag
It is known that slag chemistry has considerable can be calculated based on [O] activity in molten steel,
impact on the [O] and [S] contents in steel through 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- coefficient of j; eij the interaction parameter of i for j
lated’’ values. In the calculation, the measured a[O] and element; [pct i] and [pct j] are the weight percentage of i
temperature values at the end of the tests (Table IV) are and j in the molten steel, respectively.
used; and the activities of Al2O3 and SiO2 in the final slag A comparison of the measured activities (a[Al] and
are estimated using two approaches. The first one is by a[Si]) with the calculated values is given in Figure 8. The
using final slag chemistry (Table VII, measured with calculated activities are assumed to be equilibrated with
XRF) with the aid of the FactSage software. The slag the top slag and pure oxide, i.e., Al2O3 and/or SiO2,
equilibrium was calculated with the equilibrium module respectively. It is clear that the measured values (a[Al]
at the experimental temperature, and the activities of and a[Si]) are larger than the calculated values when steel
Al2O3 and SiO2 in liquid slagA were then obtained. The is assumed to be equilibrated with the top slag (see the
FToxide and FACT53 database are employed during the open squares and circles in Figure 8), while the mea-
estimation, and hereafter these results will be denoted as sured values are lower than the calculations with the
‘‘equilibrated with top slag.’’ The second approach is to oxide-saturated slag (see the solid squares and circles in
assume that the slag has saturated with Al2O3 and SiO2, Figure 8), and it is more obvious for the Si deoxidation
i.e., activities of the oxides (i.e., Al2O3 and SiO2) are unity reaction, i.e., Si activity in molten steel is far from the
and is indicated with ‘‘unity.’’ On the other hand, the equilibrium both with top slag and pure SiO2. This
activities of [Al] and [Si] can be obtained from Eqs. [5] indicates that (1) the slag–steel interaction did not reach
and [6][23] using compositional analysis results of the steel equilibrium during the treatment; and (2) the reactions
samples (Table VI) and interaction parameters can proceed to increase the oxide (Al2O3 and SiO2)
(Table VIII), and is denoted as ‘‘measured’’ values. The content in the slag and cease before the slag is saturated
second-order parameters are not used in the calculation with them if a longer slag–steel interaction is allowed. In
because of lack of data and their limited influence on cal- general, it is believed that the reaction has reached
culation results. equilibrium at the slag/steel interface at high tempera-
a½j ¼ f½j ½pctj ½5 ture, and this is corroborated by a number of laboratory
studies and industrial trials.[12,15,30] Therefore, there
X must be Al2O3 and SiO2 concentration gradients from
log f½j ¼ eij ½pcti ½6 the slag/steel interface toward the slag bulk. Actually,
these concentration gradients are considered to be both
where j represents the dissolved elements in molten steel; the thermodynamic and kinetic driving forces for the
a[j] the activity of dissolved element j; f[j] the activity 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 compounds, e.g., FeO, are reduced by [Al] and/or [Si] at
interaction kinetics should be investigated. the slag/steel interface (Reaction [7]). A schematic
representation of the interaction between the slag and
2. Kinetic calculations molten steel is illustrated in Figure 9. Since chemical
The slag–steel reaction kinetics can be described based reactions at the slag/steel interface at steelmaking
on a modified two-film theory[31] that the reducible temperatures are fast enough, the rate-limiting step in

METALLURGICAL AND MATERIALS TRANSACTIONS B


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 or as Eq. [10] if the rate-limiting step is the mass trans-
equation for mass transport can be expressed as port on the slag side:
Eq. [8]. d½i qs  A  ks
 ¼ fðiÞ  ðiÞ g ½10
½Al(or Si)] + FeO ! Al2 O3 ðor SiO2 Þ + [Fe] ½7 dt Wm
where A is the contact area of slag/steel interface, m2; t is
Ji ¼ ks ðCðiÞ  CðiÞ Þ ¼ km ðC½i  C½i Þ ½8 the time after the slag/alloy addition, s; Wm is the weight
of molten steel, kg; (i), (i)*, [i], and [i]* and are,
where Ji is the flux of compound i, mol/(m2 s) through respectively, the concentrations of i in the bulk of the
the slag/steel interface; km and ks are the mass transfer slag phase, at the slag/steel interface on the slag side, in
coefficient of i at the steel and slag side, respectively, m/ the bulk of the steel phase, and at the slag/steel interface
s; and C(i), CðiÞ , C[i], and C½i are the concentrations of i on the steel side, wt pct; and the qs and qm are,
in the slag, at the slag/steel interface in the slag, in the respectively, the densities of slag and molten steel at the
steel and at the slag/steel interface in the steel, respec- experimental temperature, kg/m3;
tively, mol/m3. According to Eq. [8], changes in the con- The compositional evolution in molten steel was
centration of [i] in the molten steel during the treatment computed from Eqs. [9] and [10]. Since the mass transfer
can be expressed as Eq. [9] by assuming that the rate- of [Si] in the steel phase cannot be accurately pre-
limiting step is the mass transport on the steel side: dicted—because of the different procedures for FeSi
addition, i.e., FeSi was only added in test 1, and because
d½i qm  A  km
 ¼ f½i  ½i g ½9 of the heterogeneity of the slag (dispersed Si-enriched
dt Wm 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 (i.e., through the slag/steel permanent contact reaction)
noted that the changes in [Al] during the treatment can and the mass transfer of [Al] in molten steel is
be caused by two aspects, i.e., (1) the [Al] increase due to considered to be the rate-limiting step; (2) for a given
the addition of aluminum and FeSi, and (2) [Al] test, the [Al] oxidation rate (see the slope of the
decrease owing to the slag–steel interaction. Here, the calculated curves at different times) decreases with
latter, i.e., [Al] oxidation by the reducible components in decreasing aluminum content in the steel, implying a
slag is considered. According to the literature,[12,15,30] decrease in the driving force of the reaction with the
the mass transfer of aluminum in molten steel is the rate- reaction time; (3) the calculated curves show a further
limiting step, and the mass transfer coefficient of decreasing tendency of [Al] content after around
2.0 9 104 m/s was used.[15,30] By integrating Eq. [9] 60 minutes’ treatment, indicating that the slag–steel
with respect to the slag–steel reaction time, the [Al] interactions have not reached equilibrium, i.e., the [Al]
evolution can be calculated from Eq. [11]. oxidation by the reducible component (e.g., FeO) in the
  slag would have continued if a longer slag–steel inter-
q m  A  km  t
½Al] ¼ exp  f½Al  ½Aleq g þ ½Al]eq action had been allowed. This again confirms the results
Wm of the thermodynamic analysis in Figure 8. Although
½11 there was a discrepancy in test 5, which is probably due
to an error of the [Al] measurement, the overall results in
where the equilibrated [Al]eq is used as the [Al] content Figure 11 on the prediction of the [Al] evolution during
at the slag/steel interface. Since the slag covered only the treatment suggest a promising application of the
around one fourth of the molten steel surface during the present kinetic model.
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 B. Slag–Steel–Inclusions Interaction
experimental conditions used in the calculations are 1. Sulfur content of inclusions
summarized in Table IX. As seen in Table VI, the inclusions observed in the
Figure 11 shows the calculated results of the [Al] steel samples were in the form of oxysulfides. In general,
evolution in molten steel during the treatment together the S content of an inclusion is mainly influenced by the
with the experimental data. Except for test 5, the sulfide capacity of the inclusion (C0S ) and the solidifica-
calculations are in good agreement with the experimen- tion procedure.[32,33] Since C0S is only dependent on the
tally measured values. This implies that (1) the assump- oxide composition of the inclusions and temperature,
tion of the present calculation is reasonable, in which the the C0S of the observed SiO2-MnO-Cr2O3-Al2O3 inclu-
[Al] oxidation takes place at the slag/steel interface sions can be calculated by means of the analysis results

Table IX. The Parameters Used in the Calculation of Eq. [11]

Test No. Slag Remark A (m2) km (m/s) qm (kg/m3) [Al] (ppm) [Al]eq (ppm)
1 CSF oxides 30 1
2 CA1 synthetic 40 10
3 4
3 CA oxides 4.4 9 10 2.0 9 10 7000 60 10
4 CA oxides 30 11
5 CA2 synthetic 80 17

METALLURGICAL AND MATERIALS TRANSACTIONS B


of the inclusion chemistry and the experimental tem- capacity C0S and sulfur content [S] in molten steel are
peratures. Furthermore, the equilibrated sulfur distri- known. Because (1) the equilibrated L0S is directly linked
bution L0S (= (S)incl/[S], the ratio of sulfur content with inclusion sulfide capacity, and the latter can be
between the inclusions and molten steel) can be calcu- estimated based on the oxides chemistry and experi-
lated by considering inclusion composition, experimen- mental temperature; and (2) the sulfur content in molten
tal temperature, and oxygen activity. The inclusion’s steel can be obtained from the top slag chemistry, initial
composition and experimental temperature influence the [S] content and experimental temperature,[18] the S
inclusion sulfide capacity, and the oxygen activity has content in the complex inclusions can be practically
negative effect on L0S .[18,32] The detailed calculation evaluated under steel–inclusion equilibrium conditions.
approach and discussion have been given in our However, a considerable calculation error may result if
previous paper.[18] On the other hand, the measured the inclusion-steel interaction is far away from the
L0S can be obtained from the measured sulfur content of equilibrium. As seen in Figure 12, the inclusions with
both the inclusions and the steel. Figure 12 shows the lower C0S value (log C0S < 3.0) were supersaturated
relationship between the sulfur distribution L0S and the with sulfur, while that with higher C0S value (log
inclusion sulfide capacity C0S in logarithmic form. C0S > 2.0) were undersaturated with sulfur The former
The measured and calculated equilibrated L0S values is probably because the sulfur solubility in steel
agree with each other in range of log C0S 3.0 to 2.0 decreases during the solidification, leading to further
(Figure 12). Therefore, the S content of the inclusion precipitation of MnS on the inclusions even after their
(S)incl can be calculated once the inclusion sulfide 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’’
Fig. 11—Comparison of the measured and calculated values for the
evolution of [Al] content in molten steel during the treatment.
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

Fig. 12—Relation between the sulfur distribution L0S and the inclu- 36200
2½Cr] þ 3½O] ¼ ðCr2 O3 Þincl ; log K12 ¼  16:00
sion sulfide capacity C0S , where the square and dot refer to equili- T
brated and measured sulfur distribution between inclusions and steel,
respectively. ½15

METALLURGICAL AND MATERIALS TRANSACTIONS B


It can be seen from Figure 13 that the Equilibrated ment (i.e., before top slag and alloy addition); (2) After
activity data deviate from the FactSage values if the log the FeSi and Al additions in the ladle treatment, the
a(MxOy) is higher than 1, and the discrepancy increases original SiO2-Cr2O3-Mn(O,S) type inclusions were
with increasing oxide activity. This deviation implies reduced with [Al] through the Reaction [1], resulting in
that there are large driving forces for the further steel– the Al2O3 content increase in inclusions; (3 ) The [Al],
inclusions reactions to lower the SiO2, Al2O3, and Cr2O3 meanwhile, also reacted with the reducible compounds
activities. The large deviations for the Cr2O3 and Al2O3 in the slag, decreasing the dissolved Al in the steel
activities at their saturated states (corundum existence) (Figure 11 and Table VI); , (4) Then, the reduction
are probably due to the slow steel–inclusions interac- reaction of the SiO2-Cr2O3-Mn(O,S) inclusions by the
tion. In other words, the existence of solid corundum dissolved Al slowed down and finally ceased at a certain
limits the steel–inclusions reactions. [Al] concentration, where the reduction reaction (Reac-
Based on the above experimental results (Figure 7 tion [1]) had equilibrated (Figure 7 and Table VI); and
and Table VI) and discussions (Figures 8, 11, and 13) on (5)With the further consumption of [Al] through the
the slag–steel–inclusions interactions, we propose the slag–steel interaction, the dissolved Al in liquid steel
possible mechanisms of the reactions and changes in the became so low that the newly formed Al2O3 in the
inclusion compositions during the ladle treatment as inclusions started to be reduced with [Mn], [Si], and [Cr],
follows: (1) After AOD refining, there were SiO2-Cr2O3- resulting in a slow drop in the Al2O3 content (Figure 7
Mn(O,S) inclusions in the steel before the ladle treat- 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
Fig. 13—Comparison of the calculated activities of Al2O3, SiO2, and
which the oversaturated Al2O3 in inclusion has been
MnO in the inclusions with measured values. reduced with [Mn] and [Si] in the steel, resulting in an

Fig. 14—Inclusion transformation during treatment (measured with FE-EPMA).

METALLURGICAL AND MATERIALS TRANSACTIONS B


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


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