ORIGINAL RESEARCH ARTICLE

Evolution of Non-Metallic Inclusions in Al-Killed

Stainless Steelmaking
WAN-YI KIM, GI-JU NAM, and SEONG-YEON KIM

The evolution of non-metallic inclusions (> 10 lm) for the Al-killed steel in the stainless
steelmaking is described. The effects of the slag basicity at the AOD/VOD process, Ca
treatment, raw materials (dolomite and spent refractory), reoxidation and vacuum condition on
the evolution of the non-metallic inclusion were investigated using the thermo-chemical
program (FactSageTM) and the SEM-EDS analysis of the non-metallic inclusions sampled at
each process (AOD/VOD-ladle treatment-tundish-continuous casting) and discussed for the
beneficial modification of the non-metallic inclusions to obtain better surface quality of the steel
in the secondary refining process. The phase stability diagram of the inclusion newly developed
from the analysis results and the mechanism for the evolution of non-metallic inclusion in
Al-killed stainless steel was suggested.

https://doi.org/10.1007/s11663-021-02119-4
 The Minerals, Metals & Materials Society and ASM International 2021

I. INTRODUCTION of Al and Ti would mainly evolve the CaO-SiO2-MgO

inclusion entrapped in the molten steel to the CaO-
RECENTLY, the control of non-metallic inclusions SiO2-Al2O3-MgO-TiO2 inclusion. Mapelli and Nolli[1]
has been a hot issue related to the refining process of studied the evolution of the non-metallic inclusions of 18
stainless steelmaking due to the request of many wt pct Cr- and 22 wt pct Cr-containing stainless steel
customers for high-quality steel cleanliness. In stainless using the industrial samples with Janke’s formalism[7].
steelmaking, the molten steel is deoxidized using silicon They reported that Cr2O3 formed by the addition of
or aluminum. Due to high contents of chromium (> 12 oxygen in the decarburization process would evolve to
pct) in the steel, the solubility of oxygen in the molten SiO2 or MnO-SiO2 with the addition of FeSi or SiMn
steel is much higher than that of the carbon steel. Thus, alloys. The SiO2 or MnO-SiO2 inclusions would evolve
the understanding of the evolution of non-metallic to Al2O3 with the addition of Al. Cha et al.[8] performed
inclusions in Al-killed stainless steel is crucial to control a high-temperature equilibrium experiment using an
steel cleanliness. Especially the precipitated high- induction furnace to study the evolution of inclusions
strength Al2O3 and MgAl2O4 in the inclusion in the with different Al contents in the steel, and they
Al-killed stainless steel could significantly deteriorate the emphasized the composition of the entrapped AOD
surface quality of the steel. Many researchers[1–6] have slag was easily changed to a level where the MgAl2O4
investigated the evolution of non-metallic inclusions in spinel phase can crystallize. Park et al.[3] studied the
Al-killed stainless steelmaking using the labora- Al-deoxidation equilibrium for 16 wt pct Cr-containing
tory-scale experiment or the industrial test. Kim steel and the effect of Ca treatment in Al-killed stainless
et al.[2] observed the inclusion formed as the CaO- steel using the induction furnace. They reported the
SiO2-Al2O3-MgO-TiO2 system in 304 stainless steel (18 Al2O3 inclusions formed at 60 ppm of soluble Al and the
wt pct Cr to 8 wt pct Ni) with the addition of Al and Ti Ca treatment led to CaO-Al2O3 liquid inclusions with
and studied the mechanism of the CaO-SiO2-Al2O3-M- the increase of activities of soluble Ca. Yan et al.[6]
gO-TiO2 inclusion using the BaCO3 tracer added into studied the influence of top slag in Al-killed stainless
AOD slag. MgAl2O4 and CaTiO3 phases were observed steelmaking on the evolution of non-metallic inclusions
on the inclusion, and the authors concluded the addition using a vacuum induction furnace and concluded that
the CaO-Al2O3 based slag is better than CaO-Ca-
F2-Al2O3 slag to reduce the density of the inclusions
which evolved with the following sequence after
WAN-YI KIM and SEONG-YEON KIM are with the Steelmaking addition of Al: Cr2O3-SiO2-MnO fi Al2O3-Cr2O3-
Research Group, Technical research Lab, POSCO, Pohang, Republic SiO2-MnO fi Al2O3 or Al2O3-Cr2O3. Kruger and
of Korea. Contact e-mail: [email protected] GI-JU NAM is
with the Stainless Steelmaking Technology Development Section,
Garbers-Craig[4] investigated the modification of
POSCO, Pohang, Republic of Korea. non-metallic inclusions in 409 (11 wt pct Cr) stainless
Manuscript submitted March 28, 2019; accepted February 17, 2021. steel with the addition of Ti and Ca treatment. They
Article published online March 31, 2021.

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reported that the MgAl2O4 spinel phase was observed molten slag. The molten slag and steel are tapped
with the liquid CaO-Al2O3-TiO2 inclusions in the simultaneously to the casting ladle to prevent the molten
matrix. The Ca treatment successfully modified the steel from reoxidation and absorption of nitrogen in the
crystallized MgAl2O4 spinel phase to the liquid CaO-A- air. In this case, some of the AOD slag is entrapped with
l2O3-MgO-TiO2 inclusion. Li et al.[5] analyzed the effect various sizes in the molten steel and becomes the origin
of the Al addition, Ca treatment and Ti alloy addition in of the non-metallic inclusions in the stainless steelmak-
the process on the evolution of non-metallic inclusions ing process. As shown in Table I, the composition of the
and reported the modification of inclusions after Al inclusions observed in the sample after tapping from the
deoxidation as follows: MgAl2O4 fi CaO-Al2O3-MgO AOD process is almost identical to the composition of
with Ca treatment fi CaO-Al2O3-MgO-TiO2 with Ti AOD slag. Thus, the origin of most inclusions in
alloy addition fi CaTiO3 and CaO-Al2O3-MgO phase. stainless steelmaking is the slag-entrapped inclusions.
Most researchers have focused on the Al deoxidation in The entrapped inclusions mainly evolve in the process of
stainless steel or the effect of specific treatment on the AOD-VOD (if necessary)-ladle treatment tundish by
evolution of non-metallic inclusions in the process. No various refining treatments such as the slag basicity at
systematic studies for the effects on each treatment in the AOD/VOD process, Ca treatment, raw materials
stainless steelmaking on the evolution of non-metallic (dolomite and spent refractory), reoxidation and vac-
inclusion were performed. In the present study, we will uum condition.
introduce the evolution of non-metallic inclusions in the
Al-killed stainless steelmaking process and discuss the
effects of each refining treatment on the evolution of II. EXPERIMENTAL AND ANALYSIS METHOD
inclusions in Al-killed stainless steel.
The stainless steelmaking process consists of the Samples for investigation of inclusions were prepared
EAF-AOD-LT(VOD)-CC process at POSCO as shown from the 430 grade industrial samples at each process
in Figure 1. In the EAF (electric arc furnace) process, (AOD-VOD/LT-tundish-CC). Each sampling was per-
the scrap, alloys and other raw materials are charged formed using a lollipop sampler. The lollipop is 12 mm
two or three times and melted by the electric arc within thick with 35 mm diameter. The sampling was per-
70 min. During the process, slag is formed as a formed using the argon-protected sampling system.
CaO-SiO2-based system by the addition of CaO and When the sampler reached the dipping depth in the
Fe-Si alloy under oxygen blowing. The slag formed in range of 0.5 to 0.7 m from the top surface of the molten
the EAF process is usually removed before charging to steel, the sampling was carried out to prevent entrap-
the AOD (argon oxygen decarburization) process. In ment of the top slag. Each sample was cut and polished
this process, decarburization is mainly performed with for the SEM-EDS analysis. The composition and size of
Ar/O2(g) blowing from the top and tuyere lances. The the inclusions were examined by scanning electron
quantity and ratio of Ar/O2(g) blowing are controlled microscopy (SEM) coupled with an energy-dispersive
based on the initial carbon contents in the process. The spectrometer (EDS) equipped with the INCA feature
oxidation of metallic chrome occurs with the decarbur- (Oxford Instruments, UK). Inclusions<10 lm were not
ization because of Ar/O2(g) blowing, and the formed taken into account in the present study because of the
chrome oxides are reduced by the addition of Al or FeSi lower accuracy of the EDS analysis, mainly because of
at the end of the decarburization process. Lime (CaO) the matrix effect. The measured composition of the
and Al pellets (or FeAl alloys) are added to the Al-killed inclusions was normalized with five oxide components,
stainless steelmaking, and molten CaO-Al2O3-MgO slag CaO, SiO2, Al2O3, MgO and Ti2O3. Some contents of
is formed. MgO in the molten slag is caused by the FetO and Cr2O3 could be analyzed in the inclusions, but
dissolution of the MgO-containing refractory or raw those contents were not considered because it was
materials such as dolomite added to increase the lifetime difficult to exclude the effect of the steel matrix
of the refractory. Due to the strong stirring using 6 containing 15 to 17 mass pct Cr. In addition, the
tuyeres at the reduction stage within 15 min, most of the equilibrium contents of FetO and Cr2O3 in the inclu-
deoxidation products are floated and absorbed in the sions preliminarily analyzed by thermodynamic

Fig. 1—Stainless steelmaking process at POSCO.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 52B, JUNE 2021—1509

 Table I. Composition of the Inclusion After Tapping From the AOD Process and AOD Slag

Composition [Wt Pct] CaO Al2O3 MgO Cr2O3 Fe2O3

55.67 39.23 3.54 1.45 0.11

Inclusion after tapping from AOD

AOD slag 54.17 39.74 4.59 1.07 0.43

calculation using FactSage were confirmed to be much the deoxidation products and the change of the equili-
smaller than the other components. Thus, in the present brated soluble oxygen with various chromium contents
study, the contents of FetO and Cr2O3 in the inclusion when the initial contents of aluminum and oxygen are
were negligible for analyzing the evolution of the given as 0.1 wt pct and 0.06 wt pct at 1700 C (based on
inclusion in the stainless steelmaking process. 100 tons). It should be noted that the equilibrated
The metal and slag samples were prepared for the soluble oxygen would be much lower than the soluble
chemical analysis. The contents of major components oxygen with the activity of Al2O3 = 1 because the
such as chromium, nickel, silicon, manganese, total CaO-Al2O3 slag is formed to refine the molten steel and
titanium and total aluminum were analyzed by optical absorb the alumina inclusion in the process. As Fig-
emission spectrometry, and the contents of dissolved ure 2(b) shows, the amounts of corundum (Al2O3)
aluminum, calcium, magnesium and titanium were reduce from 125 to 110 kg and the soluble oxygen
determined using a inductively coupled plasma spectro- increases from 10 to 78 ppm in the range of 0 to 30 wt
scope (ICP-AES, IRIS Advantage [REG], Thermo pct Cr at 1700 C. Thus, the molten stainless steel is
Electron, Waltham, MA). The oxygen contents were better able to keep higher soluble oxygen levels (< 10
analyzed by fusion and the infrared absorption method ppm at 1700 C) compared to the ultra-low-carbon
after very careful ultrasonic cleaning treatment. The steel, and it has more beneficial effects on the surface
composition of the slag was analyzed by an x-ray quality of the products against the reoxidation of the
fluorescence spectroscope (SRS 3400, Bruker AXS, molten steel in the process.
Cheshire, UK).
For the thermodynamic calculations, the FactPS
B. Effect of the Slag Basicity on the AOD/VOD Process
database was used to evaluate the formation of gases.
The major solution databases considered in the calcu- For the Al-killed stainless steelmaking process, the
lations were FToxid-SLAG (slag), FToxid-SPIN (spinel deoxidation and desulfurization are simultaneously
solution of MgAl2O4-MgCr2O4-MgTi2O4-FeAl2O4-Fe- performed with the addition of Al pellets or FeAl alloys
Cr2O4-FeTi2O4-Fe3O4-, etc.), FToxide-MeO (monoxide at the reduction stage of the AOD/VOD process.
solution of CaO-FeO-MgO-, etc.), FToxid-aC2S Figure 3(a) shows the effect of the slag basicity of the
(Ca2SiO4 solid solution), FToxid-CORU (corundum AOD/VOD process on the soluble oxygen and the
solution of Al2O3-Cr2O3-Fe2O3-Ti2O3) and the private activity of components in the slag at 1700 C. The data
database (liquid steel) developed at POSCO. points for the soluble oxygen obtained from 430 grade
STS show fair agreement with the calculated soluble
oxygen. It should be noted that the total oxygen
III. RESULTS AND DISCUSSION analyzed from the fusion and the infrared absorption
method was evaluated as the soluble oxygen because of
A. Effect of the Cr Contents in the Al-Killed Stainless the high solubility of the oxygen in the Cr-containing
Steel molten steel. As Figure 3(a) shows, the soluble oxygen
decreases in the range of 0.4 to 1.0 for the slag basicity
Figure 2(a) shows the deoxidation relation between
while the soluble oxygen slightly increases in the range
soluble aluminum and oxygen with various chromium
of 1.0 to 1.4. The soluble oxygen in the molten steel
contents in the molten Fe-Cr-Al-O system at 1700 C.
should be controlled as low as possible so that the
As Figure 2(a) shows, the soluble oxygen equilibrated
amounts of the deoxidation products such as Al2O3
with soluble Al = 0.05 wt pct changes steeply from 8 to
formed with decreasing temperature can be minimized.
70 ppm in the range of 0 to 30 wt pct Cr because of the
On the one hand, the activities of CaO and Al2O3 in the
strong interaction between chromium and oxygen.[9,10]
liquid slag vary with the change of slag basicity. As
Figure 2(b) shows the calculated results for the change
Figure 3(a) shows, slag with basicities > 1.0 can lower
of corundum (activity of Al2O3 = 1) contents formed as
the activities of Al2O3 in the slag with the addition of

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Fig. 2—(a) Effect of Cr contents on the soluble oxygen at 1700 C. (b) Effect of Cr on the amount of corundum (Al2O3) formed in the molten
steel (based on 100 tons) and the soluble oxygen at 1700 C.

Fig. 3—(a) Effect of slag basicity (CaO/Al2O3, CaF2 = 5 wt pct) on the soluble oxygen with the data points obtained from 430 grade (16 wt pct
Cr) and the activity of the components at 1700 C. (b) Effect of slag basicity (CaO/Al2O3, CaF2 = 5 wt pct) on the Ls (S distribution) at
1700 C with the data points obtained from 430 grade (16 wt pct Cr) and the change of liquidus temperature of the slag.

CaF2 = 5 wt pct so that the liquid slag can absorb the liquidus temperature changes to a W-shape with the slag
deoxidation products such as alumina. Figure 3(b) basicity (CaO/Al2O3). The melting points show the
shows the effect of slag basicity on the melting point minimum points at 0.6 and 1.4 (1500 C and 1400 C) in
of the slag with the addition of CaF2 as 5 wt pct. The Figure 3(a). They also show the relation between slag

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 52B, JUNE 2021—1511

basicity and Ls (S distribution, wt pct S in slag/wt pct S decreasing temperature. These evolved inclusions can
in metal) and the data points obtained from 409L grade cause severe surface defects on the steel plate or nozzle
STS. In Figure 3(a), soluble oxygen slightly increases clogging in the process. To resolve these problems, Ca
while Ls increases sharply. The soluble oxygen is treatment is performed in the ladle treatment process to
normally in the range of 15 to 30 ppm after Al modify the Al2O3-rich composition to CaO-rich inclu-
deoxidation in the stainless steelmaking process, and sions so that the inclusions can keep a fully liquid state.
thus Ls values are more sensitive to the slag basicity. In Figure 5(b) shows the evolution of the entrapped
conclusion, the difference of the soluble oxygen between non-metallic liquid inclusions from AOD to the contin-
C/A = 1.0 and 1.4 is within a few ppm while Ls values uous casting process with Ca treatment. After tapping,
increase and the activity of Al2O3 decreases as C/A the chemical composition of the inclusion sharply
increases in a given basicity range. Considering the changes toward an Al2O3-rich composition at LT arrival
lowest liquidus temperature of the slag, CaO/Al2O3 = and LT departure. Without the Ca treatment, the
1.4 would be the best choice for the process. composition of the inclusion will dramatically evolve
toward an Al2O3-rich composition with decreasing CaO
contents in the inclusion as shown in Figure 4(b) (CaO
C. Effect of the Ca Treatment
= 9.64 pct), and finally the corundum (Al2O3) or spinel
In the steelmaking process, Al2O3-rich non-metallic (MgAl2O4) will be formed. However, due to the Ca
inclusions are well known to generate surface defects treatment carried out at 1590 C as shown in Fig-
and nozzle clogging[11–13] as shown in Figure 4. Fig- ure 5(b), the contents of CaO in the inclusion are
ure 4(b) shows the network connected spinel phase increased by the reaction with MgO and Al2O3 in the
(MgAl2O4) on the cross section of the clogging part. In inclusion so that the inclusion can maintain a fully liquid
the stainless steelmaking process, as mentioned previ- phase at the tundish and mold.
ously, the molten steel is poured simultaneously with the
molten slag to prevent the absorption of nitrogen and
oxygen from air. The soluble oxygen can be changed D. Effect of the Raw Materials (Dolomite and the Spent
after tapping in the range of 30 to 60 ppm because of the Refractory)
absorption of the oxygen from the air. The initial The composition of raw materials should be strictly
composition of the entrapped inclusions is very similar managed because the trace elements in the raw materials
to the composition of AOD slag, which is the can have a significant effect on the modification of
CaO-Al2O3-MgO system. The initial composition of non-metallic inclusions. The raw materials such as
the entrapped inclusions is significantly changed because dolomite (CaO-MgO) and the MgO-rich spent refrac-
of their small size (10 to 20 lm) and the reaction with tory (MgO > 70 pct) used as the refractory of the AOD
the molten steel. The composition of inclusions is furnace are added to the slag to maintain the longer
sensitively affected by soluble Ca, Al and Mg in the lifetime of the refractory in the AOD process. Consid-
molten steel with decreasing temperature. Figure 5(a) ering the typical size of the inclusions (10 to 20 lm), a
shows the evolution of non-metallic inclusions obtained few ppm of oxygen or other soluble elements such as Al,
from industrial samples without Ca treatment from Ca, Mg and Ti in the molten steel are enough to modify
AOD to the continuous casting process for Al-killed the inclusions with decreasing temperatures because of
stainless steel. Due to the high potential of soluble Al in the mass balance between the molten steel and the
the range of 500 to 800 ppm, the entrapped non-metallic inclusion. On the other hand, the meltability of the raw
inclusions in the molten steel after tapping evolve materials is also very important to maintain better
toward an Al2O3-rich composition, which can precipi- cleanliness of the molten steel. Figure 6 shows the
tate corundum (Al2O3) or spinel (MgAl2O4) phases with results of SEM analysis for the inclusions from AOD to
tundish in the Al-killed stainless steel with the addition
of the MgO-rich spent refractory. Each inclusion from
AOD to LT departure contains high MgO contents
because of the presence of MgO(s) particles. Interest-
ingly, the inclusion contains both MgAl2O4(s) and
MgO(s) at tundish while other inclusions from AOD
to LT departure have no spinel MgAl2O4 phases.
Figure 7 shows the calculated phase diagram of the
CaO-SiO2-MgO and the CaO-Al2O3-MgO system com-
pared to the measured data at 1700 C in the AOD
process without the addition of the MgO-rich spent
refractory. As Figures 7(a) and (b) show, the solubility
of MgO in the CaO-SiO2 system is much higher in the
wide range of the slag basicity than that of the
CaO-Al2O3 system. Furthermore, the SEM-EDS anal-
ysis of the inclusions obtained in Si-killed steel
Fig. 4—Nozzle clogging of the Al-killed stainless steel. (a) SEN
(submerged entry nozzle) image. (b) SEM image on the cross section
(CaO-SiO2-MgO system) shows undissolved MgO(s)
of the clogging part and the oxide inclusions identified as the spinel while the inclusions sampled in Al-killed steel (CaO-A-
(MgAl2O4) network. l2O3-MgO system) still contain undissolved MgO(s).

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Fig. 5—(a) Phase diagram of the CaO-MgO-Al2O3 system with the measured data (AOD to slab) plotted on the isothermal section from
1400 C to 1800 C. (b) Simulation of the evolution of non-metallic inclusions in the Al-killed steel compared to measured data at each process.

Fig. 6—SEM analysis of the inclusions obtained from the process of AOD to tundish in the Al-killed steel with the addition of MgO-rich spent
refractory.

The composition of the liquid phase and the average implies that the addition of the Al pellet, CaO and CaF2
composition of the inclusion are separately plotted in at the reduction stage dissolves the MgO-containing
the phase diagram of the CaO-Al2O3-MgO system in refractory, and some undissolved MgO(s) particles
Figure 7(b). Notably, the average composition of the remain because of the low solubility of MgO in the
inclusion is mainly located in L + monoxide (MgO-rich molten CaO-Al2O3-CaF2 system. After tapping, the
solid solution) or L + monoxide #1 + monoxide #2 slow kinetics of the dissolution of MgO(s) particles in
(immiscibility gap between CaO-rich and MgO-rich the entrapped inclusions will keep the MgO(s) particles
monoxide solid solution) while the composition of the in the process. The remained MgO(s) particles can
liquid phase in the inclusion containing < 4 wt pct MgO precipitate MgAl2O4 spinel phase in the inclusion with
is located in the fully liquid region. Figure 8 shows the decreasing temperatures because of the high activities of
enthalpy of the mixing in the binary system at 1700 C. Al2O3(s) and MgO(s) in the inclusion. Park et al.[14]
Mostly the main slag system in the AOD process investigated the dissolution behavior of MgO particles
consists of CaO-Al2O3-MgO or CaO-SiO2-MgO sys- in the CaO-Al2O3-SiO2 slag system using a high-tem-
tems. Comparison of the enthalpy of mixing for the each perature confocal scanning laser microscope and
binary system at a certain temperature could give observed the ring-like structure of MgAl2O4 spinel
qualitative estimation for the meltability or solubility phase locally equilibrated with the liquid slag and the
of MgO(s) in the slag more or less. As Figure 8 shows, MgO(s) particles. The composition of the liquid slag
the CaO-SiO2 and the CaO-Al2O3 systems show much phase located between the MgO(s) particles, and the
stronger solution forming behaviors than the MgO-SiO2 ring-like structure of MgAl2O4 showed a co-saturation
and the MgO-Al2O3 systems. Especially the enthalpy of state with the MgO(s) and MgAl2O4 phase. These results
mixing between the CaO-SiO2 and the MgO-Al2O3 correspond to the results of the present study. After all,
systems shows a large difference as 41100J/mol. This the undissolved MgO(s) particles in the entrapped

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Fig. 7—(a) Calculated phase diagram of the CaO-SiO2-MgO system at 1700 C with SEM-EDS results of the inclusion at the reduction stage of
AOD in Si-killed stainless steel. (b) The CaO-Al2O3-MgO system at 1700 C with SEM-EDS results of the inclusion at the reduction stage of
AOD in the Al-killed stainless steel.

reoxidation products could form very easily if there were

any oxygen sources from the air or the ladle filler
(Fe2O3-Cr2O3-SiO2). These reoxidation products could
bring serious surface defects to the slab or coil products.
Figure 9 shows the results of SEM-EDS analysis for the
inclusion on the defect side of the coil and the
calculation results for the evolution of the reoxidation
products at 1520 C with the measured data (average
composition). No liquid phase in the inclusion was
observed, and the only solid phase of the Al2O3-Cr2O3-
TiO2 was identified from SEM-EDS analysis. The
thermodynamic calculation with the change of oxygen
potential suggests that the equilibrated phase in the
inclusion is corundum (Al2O3-Cr2O3) and TiO2(s) phase.
This implies that the steel could be re-oxidized on the
surface of the metal because the oxygen potential is >
Fig. 8—Enthalpy of mixing in the binary system at 1700 C. 10-8 atm, which could be caused by leaking of some part
on the shroud nozzle or other parts in the tundish. The
inclusion could evolve to the MgAl2O4 spinel phase with oxygen sources could be removed by the purging of inert
decreasing temperature, and this could cause problems gas (Ar or N2) containing low oxygen gas potential.
such as the nozzle clogging in the process.
F. Effect of the Vacuum in the Process
E. Effect of the Reoxidation at Tundish
Some stainless steel grades are required to reduce the
Some stainless steels should contain large amounts of carbon contents as much as possible (<100 ppm) so that
Ti (> 0.2 wt pct) and Al (> 0.15 wt pct) with high the physical properties of the steel are satisfactory for
chromium contents (> 20 wt pct). Using the thermody- the customer. To reduce the carbon contents, if neces-
namic calculation by FactSageTM, we confirmed that the sary, the VOD (vacuum oxygen decarburization) pro-
soluble oxygen in the molten steel could increase up to cess is applied. The VOD process consists of three
260 ppm at 1520 C because of the high chromium stages: (1) oxygen blowing; (2) degassing; (3) reduction.
contents (Cr = 20 wt pct) while the soluble oxygen in The initial carbon contents in the VOD process are in
the steel could reduce up to 3 ppm with the addition of the range of 0.2 to 0.6 wt pct while the Cr contents are in
Ti (> 0.2 wt pct) and Al (> 0.15 wt pct). Thus, the the range of 11.0 to 25.0 wt pct. Thus, Cr oxidation

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Fig. 9—(a) SEM analysis for the inclusions on the defect side of 22 wt pct Cr-0.25 wt pct Ti-0.3 wt pct Al and (b) the calculation results for the
evolution of the reoxidation products in tundish at 1520 C with the data point (average composition).

Fig. 10—Effect of the vacuum on the evolution of non-metallic inclusion: (a) change of the MgO contents in the inclusion at each process; (b)
SEM analysis of the inclusion in the sample obtained from tundish.

simultaneously occurs under the vacuum condition (< inclusion. Figure 10(a) shows the change of the MgO
300 mbar) with decarburization at the oxygen blowing contents in the inclusion with the SEM analysis results.
stage. At the degassing stage, the total pressure is The contents of MgO significantly increase from VOD
controlled below 60 mbar under oxygen blowing to departure to tundish (+21 pct) in the inclusion. The
reduce the carbon contents under 100 ppm. Tempera- precipitated spinel (MgAl2O4) and MgO(s) in the sample
ture of the molten steel is changed in the range of obtained from tundish are shown in Figure 10(b). This
1550 C to 1750 C in the process. Plenty of Cr oxides unique increase of MgO contents in the inclusion is not
formed from the oxygen blowing stage to the degassing observed for the steel grade finished with only the AOD
stage are reduced with the addition of reducing agents process (see Section III–C and Figure 5). Figure 11(a)
such as Al- or Si-containing alloys. At the reduction shows the calculated standard Gibbs free energy for the
stage, for the Al-killed stainless steel, the CaO-A- formation of Mg gas by soluble Al and the amounts of
l2O3-MgO slag system is formed by the addition of the Mg(g) with the change of the total pressure at
CaO, dolomite (CaO-MgO) and Al pellets. During the 1700 C. The formation of Mg(g) occurs abruptly below
reduction stage, many slag droplets are entrapped in the 10-3 atm as the total pressure. Thus, as shown in
molten steel and become the origin of the non-metallic Figure 11(b), the added Al can reduce the MgO from

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Fig. 11—(a) Calculated standard Gibbs free energies for the formation of Mg (g) by the soluble Al in the steel and the amounts of Mg (g) with
the change of total pressure. (b) Mechanism for the formation of Mg (g) from the dolomite refractory under vacuum (< 60 mbar).

the dolomite (CaO-MgO) or MgO-C refractories to the co-saturation of Al2O3(s)-MgAl2O4(s) or

form Mg(g) under vacuum conditions (< 10-3 atm), and MgO(s)-MgAl2O4(s) under the given soluble Mg and
the formed Mg(g) will dissolve in the molten steel as Al contents. Their phase stability diagrams could only
soluble Mg. The increase of soluble Mg can have a explain the deoxidation products of MgO, Al2O3 and
significant effect on the increase of MgO contents in the MgAl2O4 spinel phase equilibrated with soluble Mg, Al
inclusion after the process with decreasing temperatures. and oxygen in the molten steel while the evolution of the
entrapped inclusions for the Al-killed stainless steel
could not be taken into account.
G. Phase Stability Diagram for Inclusions
in the Al-Killed Stainless Steel 4Al2 O3 ðs) + 3Mg ¼ 3MgAl2 O4 ðs) + 2Al ½1
Some researchers have studied the build-up of the
phase stability diagram for Al-killed stainless steel using
the FactSage thermochemical program or the standard 4MgO(s) + 2Al ¼ MgAl2 O4 ðs) + Mg ½2
Gibbs free energy changes of the reaction with interac-
tion parameters obtained from Wagner’s formalism in The newly drawn phase stability diagram for Fe-17 wt
relation to the spinel formation[9] for the inclusion in pct Cr at 1550 C using the thermodynamic database
Al-killed stainless steel[15,16] to estimate the evolution of mentioned in Section II under the assumption of a
non-metallic inclusions at a given soluble Mg, Al and singular route for the formation of spinel MgAl2O4
oxygen in the system. Park and Todoroki[15] built up the without Ca treatment is shown in Figure 12(a) with the
phase stability diagram for the inclusion in Al-killed soluble oxygen contents and measured data points. No
stainless steel under the assumption that the local inclusions are formed when both soluble Al and Mg are
equilibrium between the MgO and Al2O3 inclusions in < 10 ppm under the assumption of a singular route for
the molten steel in the formation route of singular spinel the formation of spinel MgAl2O4 even though the
inclusions is only of MgAl2O4 as shown in Eqs. [1] and soluble oxygen is > 100 ppm. On the other hand, the
[2]. The formation of singular spinel inclusions assumes liquid inclusion of the CaO-Al2O3-MgO system is shown

1516—VOLUME 52B, JUNE 2021 METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 12—Calculated phase stability diagram at 1550 C under the assumption of (a) a singular route for the formation of spinel MgAl2O4 only
with the SEM analysis results for the inclusion obtained from tundish; (b) the evolution of the entrapped inclusions containing the
CaO-Al2O3-MgO system with the SEM analysis results for the inclusion obtained from tundish.

in Figure 12(b). It should be noted that the liquid mechanism for the evolution of inclusion in the Al-killed
inclusion of the MnO-SiO2-CrOx system could form as stainless steel as shown in Figures 13 and 14 is believed
the soluble oxygen is > 480 ppm in the austenitic to be as follows. Cr oxidation significantly occurs under
stainless steel containing 18 pct Cr-8 pct Ni-1.1 pct oxygen blowing in the decarburization process, and
Mn-0.4 pct Si. As Figure 12(a) shows, most of the data CrOx is reduced by the addition of Al pellets in the
points obtained from the industrial plant are distributed deoxidation process. The deoxidation products for the
on the Al2O3(s) + spinel, Mg[Al,Cr]2O4 stable region. Al-killed stainless steel are different from the Al-killed
Most inclusions, as shown in Figure 5(a), are evolved carbon steel because of high amounts of chrome. The
from the CaO-Al2O3-MgO system with the liquid phase equilibria for the Al-deoxidation for Fe-25 pct Cr-2 pct
with formation of spinel or Al2O3(s) with high potential Si-0.7 pct Mn and Fe-20 pct Cr-10 pct Ni melt in the
of the soluble Al with decreasing temperatures. Fig- temperature range of 1550 C to 1600 C, which was
ure 12(b) shows the newly developed phase stability studied by Heinz[22] and Fischer and Janke,[23] respec-
diagram with Ca treatment (Ca = 5 ppm) under the tively. These authors[22,23] reported the deoxidation
assumption that the inclusion would evolve from the product was the Al2O3-Cr2O3 solid solution (corundum)
entrapped calcium aluminate inclusion containing a few phase. Figure 13(a) shows the change of soluble Cr, Al
wt pct of MgO in the molten steel, which is suggested to and oxygen contents with the addition of Al pellets in
take into account the stable phase with the given soluble the deoxidation process. As Figure 13(a) shows, the
Mg, Al and oxygen. The measured data points obtained soluble Cr completely recovers with the addition of Al
from the Ca-treated molten steel are located on L + pellets when the soluble Al and the soluble oxygen at
spinel, the Mg[Al,Cr]2O4 stable region, and are in good 1700 C are 152 and 95 ppm, respectively. The soluble
agreement with the analysis results obtained using the oxygen decreases by 64 ppm with the soluble Al = 550
SEM-EDS as shown in Figures 12(a) and (b). ppm for complete deoxidation at 1700 C. Due to ideal
solution behavior between Al2O3 and Cr2O3,[24] the
Cr2O3 reduces linearly with the addition of Al pellets as
H. The Mechanism for the Evolution of Inclusion
shown in Figure 13(b). To decrease the activity of Al2O3
in Al-Killed Stainless Steel
formed in the deoxidation process and the equilibrated
Many authors[12,13,17–21] believed that non-metallic soluble oxygen as mentioned in Section III–B, CaO or
inclusions in Al-killed stainless steel evolve on the dolomite (CaO-MgO) is added to form the CaO-A-
formation route of singular spinel consisting only of l2O3-MgO slag system at the AOD or VOD process.
MgAl2O4. However, in the present study, the analysis During the tapping at the AOD or the reduction stage
results using Auto-SEM confirmed that most inclusions during the VOD process, at first, numerous slag droplets
(> 99 pct) were calcium aluminate (CaO-Al2O3) with are entrapped into the molten steel because of the strong
some amounts of MgO and evolved to precipitate the turbulence between slag and molten steel. Due to the
spinel (MgAl2O4) or CaAl2O4 phase in the inclusion vigorous stirring by Ar gas at the reduction stage, the
depending on the conditions of the process. The equilibrium between molten steel and slag could reach a

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 52B, JUNE 2021—1517

Fig. 13—(a) Calculated evolution of soluble elements (Cr, Al and oxygen) with the addition of Al. (b) Composition change of corundum
(Al2O3-Cr2O3) phase under the reduction stage at 1700 C.

certain level of soluble Al, Mg and Ca in the molten 1. AOD/VOD process: slab basicity, tapping tempera-
steel. These soluble elements (Ca, Al, Mg) react with the ture and vacuum condition
entrapped inclusions. It should be noted that the soluble 2. LT arrival: impurities (Al, Ca, Mg, O) from the
Al for the Al-killed stainless steel could be higher than coolants and ladle glazing on the casing ladle, raw
the several orders of magnitude compared to soluble Ca material usage (high-MgO containing refractory)
and Mg. Thus, the reactions in Eqs. [3] and [4] are 3. LT departure: Ca treatment (Ca-containing material
predominant between the molten steel and the inclusion and bubbling time)
with decreasing temperature. The contents of soluble 4. Tundish: reoxidation (air suction from the shroud
Mg would depend on the amounts of MgO in the slag nozzle, ladle filler and any oxygen source)
and the tapping temperature at AOD. Especially, the 2Al + 3(MgO)Inclusion = (Al2 O3 ÞInclusion þ3Mg ½3
soluble Mg could significantly increase under the vac-
uum condition because of the reaction in Eq. [5] in the
VOD process as mentioned in Figures 10 and 11.
Soluble Ca could be supplied from CaO or CaF2 in 2Al + 3(CaO)Inclusion = (Al2 O3 ÞInclusion þ3Ca ½4
the slag or from the Ca treatment at ladle treatment as
shown in Figure 5. After Ca treatment, soluble Ca
increases and reacts with Al2O3 and MgO in the 2Al + 3(MgO)Refractory = (Al2 O3 ÞInclusion + 3Mg(g)
inclusion as described in Eqs. [6] and [7]. Thus, proper
Ca treatment could have a diluting effect on the ½5
amounts of Al2O3 and MgO in the inclusion so that
the precipitation of MgAl2O4 or Al2O3 phase in the
inclusion could be suppressed. 3Ca + (Al2 O3 ÞInclusion = 3(CaO)Inclusion þ2Al ½6
Figure 14 describes the mechanism for the evolution
of non-metallic inclusions observed from the present
study. In conclusion, we suggest that the following
Ca + (MgO)Inclusion = (CaO)Inclusion þMg ½7
factors are important to control the evolution of
non-metallic inclusions in the Al-killed stainless steel-
making process

1518—VOLUME 52B, JUNE 2021 METALLURGICAL AND MATERIALS TRANSACTIONS B

 MgO dissolution from the refractory: Slag basicity and Vacuum condition

Raw material effect : Dolomite and MgO-rich spent refractory ȥ Presence of MgO

particle in the inclusion

Soluble Al and Mg : Slag basicity (wt% MgO in Slag) and Tapping temperature

Increase of soluble Mg : Mg(g) formation by soluble Al from the refractory containing

MgO under the vacuum condition

Soluble Ca : Ca-treatment (CaSi wire or lump)

Reaction between Inclusion and Soluble elements (Ca, Mg and Al)

Fig. 14—Mechanism for the evolution of non-metallic inclusions (> 10 lm) and the critical factors at each process in the Al-killed stainless steel.

IV. CONCLUSIONS 2. LT arrival: impurities (Al, Ca, Mg, O) from the

coolants and ladle glazing on the casing ladle, raw
In the present study, the evolution of non-metallic material usage (high-MgO containing refractory)
inclusions (> 10 lm) in the Al-killed stainless steelmak- 3. LT departure: Ca treatment (Ca-containing material
ing process is studied. The effects of the slag basicity in and bubbling time)
the AOD/VOD process, Ca treatment, raw materials 4. Tundish: reoxidation (air suction from shroud noz-
(dolomite and spent refractory), reoxidation and vac- zle, ladle filler and any oxygen source).
uum on the evolution of the non-metallic inclusions
were analyzed using the thermo-chemical program
(FactSageTM) and SEM-EDS analysis of the non-metal-
lic inclusion in each process (AOD/VOD-ladle treat-
ment-tundish-continuous casting). In the obtained
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