Metall. Res. Technol.

114, 211 (2017)

© EDP Sciences, 2017 Metallurgical Research
DOI: 10.1051/metal/2017028 &
Technology
Available online at:
www.metallurgical-research.org

REGULAR ARTICLE

Formation of MgO-based inclusions during AOD and ladle

treatment of Al-killed 2205 duplex stainless steel
Zongxu Pang1,2, Rong Zhu1,2,*, Peidun Chen1,3, and Zhen Wang1
1
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083,
P.R. China
2
Beijing Key Laboratory of Special Melting and Preparation of High-end Metals, Beijing 100083, P.R. China
3
Shandong Taishan Steel Group Co. Ltd., Laiwu 271100, P.R. China

Received: 21 November 2016 / Received in final form: 11 March 2017 / Accepted: 27 March 2017

Abstract. Pilot trials were performed to study the formation mechanism of MgO-cored inclusions in 2205
stainless steel refined using low-Al high-basicity slag. The composition of melts and slags significantly affected
the inclusion types, compositions, and shapes. Experimental results showed characteristic CaO and MgO dual-
saturation in the slags. The compositions of the inclusions approached those of the slags, viz. the MgO-rich MgO-
spinel solid solutions or pure MgO. MgO in the slags provided sufficient Mg to the steel melts that newly
generated pure MgO stably approached equilibrium as the Mg–O deoxidization reaction continued. The activity
changes of Ca, Mg, and Al during refining were modeled. The activity of Mg exceeded those of Al and Ca, and the
Mg–O reaction was always dominant. A kinetics model was established to elucidate the changing mechanisms of
inclusions. The transferring kinetics of inclusions was discussed qualitatively to analyze velocity-controlled steps.
The concentration of Al was low in molten steel, implying a low potential energy of Al3+ and impeded diffusion into
the MgO core to form MA-spinel. Meanwhile, the diffusion of Mg2+ into the MgO core was the rate-limited step.
Keywords: duplex stainless steel / MgO-based inclusions / evolution mechanisms / FactSage

1 Introduction compared with FSS, DSS still retains 475 °C brittlement,

Duplex stainless steel (DSS) is a typical steel of composite
metallographic structure. Compared with 304 steel as a
representative of austenitic stainless steel (ASS), resistance
to local corrosion (pitting, crevice corrosion, corrosion
fatigue, stress corrosion cracking, etc.) performance is
superior and has higher strength and lower nickel consump-
tion. Compared with 430 steel as a representative of ferrite
stainless steel (FSS), it has higher toughness and a lower
brittle transition temperature. In addition, resistance to
intergranular corrosion and welding performance are
significantly improved. There have been a large number of
DSS instead of ASS and FSS.
However, compared with ASS and FSS, DSS still has
some weaknesses. First, plastic and toughness are lower
than those of ASS, and the tendencies of the work-
hardening effect in DSS were more obvious than those in
ASS. At the beginning of a deformation, it is necessary to
exert a large force to deform the tube and plate, which
produces more inner stress and thus makes hot working
processing more difficult than that for 304 ASS. Second,
* e-mail: zhurong@ustb.edu.cn
s phase precipitation, etc. However, DSS contains a large
amount of solute nitrogen, The remaining elements in melts,
such as titanium after alloying, are easy to form a large
amount of TiN, then polymerize into large TiN inclusions,
significantly increasing the brittleness. A laboratory
study [1] on 16% Cr ferritic stainless steel discovered that
the oxides in steel ingots was observed to be covered by
TiN when the Mg/Al mass ratio of oxides ranged from 0.3 to
0.5. It is speculated that the spontaneous nucleation of
liquid Al–Mg–Ti oxide occurs owing to low interfacial
energy with molten steel. Therefore, the type of MgO-riched
MgO–Al2O3 solid solution in melts is conducive to
suppressing the polymerization of TiN inclusion. In addition,
MgO · Al2O3 spinel had very high interfacial energy and
was prone to agglomerate and grow, while the interfacial
energy of MgO was relatively low and the sintering property
of MgO was worse than that of MgO–Al2O3 spinel.
Therefore, MgO was unlikely to cause nozzle clogging or
the agglomeration of large MgO-based inclusion particles. In
consideration of the contact angle (u) between Fe–Cr melts
and pure MgO or Al2O3 inclusions, Park and Kim [2]
concluded that the probability of cluster formation of Al-rich
inclusions in Fe–Cr melts was larger than that of MgO-rich
inclusions.
2 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017)
The spinel inclusions in stainless steel are usually
considered as single MgO–Al2O3 spinel phases that form
directly in liquid steel, and/or as spinel crystals that
precipitate from CaO–SiO2–MgO–Al2O3 liquid droplets
during solidification [2–11]. In recent years, more studies
have focused on MgO-rich MgAl2O4 spinel. The typical
morphology of inclusions in Fe–16Cr melts was analyzed by
Park and Kim [2] in phase equilibrium with high-basicity
slags with CaO and MgO oversaturated in CaO–Al2O3–
MgO systems. The MgO content in these inclusions was
50% in the core and decreased to approximately 35% at the
edge. Todoroki and Mizuno [12] showed that the SiO2
content in CaO–SiO2–MgO–Al2O3–F system slags did not
affect the formation of MgO–Al2O3, but it did react with
MgO and CaO in slags. Therefore, the Mg reduced from
slags was insufficient to contribute to the further
transformation from MgO–Al2O3 into MgO or CaO–
Al2O3–MgO systems. Some scholars [7,8,11] drew a similar
conclusion that inclusions containing CaO can coexist with
those containing MgO, thus will not form MgO-core
inclusions. However, other papers [13–15] showed that
MgO-based inclusions were typical, in addition to MgO–
Al2O3, in Al-killed stainless steel.
At present, nearly all researchers agree that refining
slags containing MgO are dominant in the origin of Mg
necessary for spinel formation. The formation of MgO–
Al2O3 should be inevitable because of the high content
of balanced Al in molten steel, which could reduce the
MgO content of slags. However, this understanding
could not properly explain the phenomenon in which
many inclusions containing MgO in the core and MgO–
Al2O3 segregated outside in molten steel are formed
early in ladle furnace (LF) reduction practices. By
analyzing plant trial data and thermodynamics analysis,
as well as analysis by the un-reacted core model, the
evolution mechanisms of high-melting-temperature
solid inclusions into relatively lower-melting-tempera-
ture inclusions were elucidated, as presented in detail in
this article. In addition, the origin of Mg and the
formation mechanism of MgO-core inclusions in molten
steel are also explained.
2 Materials and methods
2.1 Experimental procedure and sampling
An industrial trial was performed in a stainless steel plant.
The steelmaking process featured “argon-oxygen decarbu-
rization (AOD) steelmaking ! LF refining ! slab casting”.
CaO, Fe–Si alloy, and Al were added to the molten steel for
deoxidizing and slagging during the reduction of AOD. The
molten steel was then transferred to the LF station. A
relatively high-basicity slag was used during LF refining.
To investigate the evolution of MgO-based inclusions,
liquid steel samples were taken from the melt with bucket
samplers at the initial stage of AOD deoxidization
(AOD1), AOD departure (AOD2), LF arrival (LF1),
and LF departure (LF5). In addition, three samples were
taken during the LF refining periods at intervals of
approximately 15 min (LF2 ∼ LF4).
2.2 Analysis of steel and slag samples
Steel and slag samples were prepared for chemical analysis,
as listed in Tables 1 and 2, respectively. The conventional
elements identified using spectral analysis, acid-soluble Al,
T.Ti, T.Ca, and T.Mg content in steel, were analyzed by
inductively coupled plasma-atomic emission spectroscopy.
The total oxygen contents in the samples were determined
by fusion and the infrared absorption method. The
composition of the slags was analyzed by ethylenediami-
netetraacetic acid complexometry. The chemical compo-
sitions in this article are all given in mass percentage. Steel
samples for inclusion analysis were also prepared. Inclu-
sions on the cross sectioned plane of each steel sample were
detected and analyzed by scanning electron microscopy
(SEM) with energy-dispersive X-ray spectroscopy to
obtain information about the inclusions, such as morphol-
ogy, size, and chemical compositions, etc.
3 Results
3.1 Chemical compositions of steel and slag
The chemical compositions of the steel and slag are given in
Tables 1 and 2, respectively. The cleanliness of steel is
higher after LF refining with S contents of ∼0.002–0.003%,
and the (FeO + MnO) content in slag is low. CaO and SiO2
are present at levels of ∼48.89–53.73% and ∼19.10–19.99%,
respectively.
3.2 Change of inclusion type during refining process
All typical detected inclusion types from each manufactur-
ing stage, as well as the distribution of the main elements in
these different inclusions, are shown in Table 3. Three
categories of inclusions are observed: MgO-based, MgO–Al2O3
system, and CaO–MgO–Al2O3 system inclusions. MgO-based
inclusions refer to those with high MgO contents, or even
pure MgO. Notably, MgO-based inclusions and MgO–Al2O3
system inclusions do not exist as separate phases, which occur
with the spinel or Al2O3–CaO–SiO2 systems. Typical SEM
images and elemental mapping of the different types of
inclusions are shown in Table 3. All detected inclusions are
small in size, within 3–5 mm. Most inclusions are globular in
shape, implying that they were liquid in state in the molten
steel at steelmaking temperatures.
The mapping results of the evolution of inclusions in
refining process are illustrated by Table 3 and can be
described as follows:
– AOD reduction: Because no Al2O3 inclusions wrapped by
MgO–Al2O3 (MA spinel) layers are found, the trans-
forming speed from Al2O3 into complete MgO–Al2O3 is
assumed rapid. As a result, inclusions at AOD reduction
are mainly in the MgO–Al2O3 and Al2O3–CaO–SiO2
systems. Notably, the MgO content in MA-spinel
increases gradually after AOD tapping. The fraction of
CaO in the liquid Al2O3–CaO–SiO2 system increases
gradually, while the fraction of SiO2 gradually decreases.
– AOD tapping: After AOD tapping, Al reacts with CaO
and MgO in slags during slagging effect, the fraction of
CaO and MgO in inclusions increases, and the new liquid
 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017) 3

Table 1. Chemical compositions of molten steel after experiments (mass %).

Smelting stage C Si Mn Cr Ni Mo S T.O T.Ti T.Ca T.Mg Als

AOD reduction 0.019 0.50 0.88 22.79 4.95 3.02 0.003 0.0031 0.0023 0.0022 0.00080 0.0055
AOD tapping 0.024 0.51 0.91 22.98 4.86 3.06 0.002 0.0037 0.0024 0.00289 0.00078 0.0041
LF arrival 0.024 0.49 1.07 23.02 4.96 3.04 0.002 0.0028 0.0026 0.00385 0.00327 0.0067
LF 21 min 0.022 0.52 1.08 22.90 4.91 3.06 0.002 0.0020 0.0024 0.00118 0.00074 0.0054
LF 35 min 0.026 0.52 1.08 22.74 5.04 3.08 0.002 0.0018 0.0031 0.00095 0.00069 0.0048
LF 55 min 0.024 0.51 1.07 22.87 5.10 3.05 0.002 0.0018 0.0053 0.00083 0.00080 0.0051
LF departure 0.027 0.52 1.08 22.85 5.08 3.07 0.002 0.0018 0.0053 0.00080 0.00085 0.0052

Table 2. Chemical compositions of slag after experiments (mass %).

Smelting stage SiO2 MnO MgO TiO2 Al2O3 CaO CaF2 FeO Cr2O3 Fe2O3
AOD reduction 19.89 0.07 7.20 0.53 9.77 52.29 9.83 0.21 – 0.21
AOD tapping 20.06 0.06 7.57 0.53 9.43 53.73 8.26 0.12 0.08 0.15
LF arrival 19.99 0.06 6.95 0.49 9.79 53.57 8.63 0.19 0.19 0.13
LF 21 min 19.50 0.05 6.51 0.36 7.69 49.64 15.44 0.38 0.08 0.36
LF 35 min 19.10 0.05 6.30 0.38 8.11 48.89 16.30 0.49 0.04 0.34
LF 55 min 19.14 0.04 6.03 0.36 8.14 49.22 16.70 0.12 0.03 0.22
LF departure 19.20 0.04 5.60 0.38 8.15 49.41 17.04 0.10 0.02 0.06

Al2O3–CaO–SiO2 and MA spinel systems are generated.
The inclusions are mainly divided into two categories.
(1) On the outside of spherical liquid Al2O3–CaO–SiO2
systems, MgO is distributed evenly in a ring shape; and
(2) MA spinel is wrapped partially by the liquid Al2O3–
CaO–SiO2 system.
– LF arrival: The number of inclusions with ring-shaped
MgO begins to decrease; meanwhile, pure MgO inclu-
sions are formed. Almost all newly generated polygonal
MgO collides with liquid Al2O3–CaO–SiO2 and aggre-
gates together, so that the general morphology of
inclusions is spherical.
– LF 21 min: The inclusions with ring-shaped MgO
disappear because almost all of them are transformed
into inclusions with segregated MgO. Compared with LF
arrival, the dimension of pure MgO increase and no MA
spinel inclusions wrapped with ring-shaped MgO are
found, indicating that the growth of pure MgO is caused
by the direct reaction between Mg and the dissolved
oxygen in the molten steel.
– LF 35 min: The dominant inclusion type remains pure
MgO segregated inclusions, while the dimensions of MgO
continue to increase. Notably, inclusions with MgO cores
appear at this time. On the outside of these inclusions are
CaO–Al2O3 solid phases with high Al2O3 contents; SiO2
continues to decrease.
– LF 55 min: The outer layer composition of the inclusions
changes significantly at this time. The SiO2 content in
the Al2O3–CaO–SiO2 system decreases further, while the
CaO content increases. In addition, the morphology of
the inclusions changes: the angular outer layer tran-
sitions to a smooth surface and the fraction of liquid
phase in the inclusions increases.
– LF departure: The dimensions of the MgO cores of
inclusions increases further after LF departure. These
remain surrounded by outer ring-shaped CaO–Al2O3
systems, in which approximately 5% SiO2 remains in the
outer liquid inclusions. This indicates that the oxygen
potential energy remains slightly high, and the activity of
Ca remains lower than that of Mg. Therefore, Ca cannot
diffuse into the inner core of MgO inclusions, and only reacts
with Al2O3 to form liquid CaO-rich Ca–Al inclusions.
3.3 Change of inclusion composition during refining
process
The sample was analyzed automatically with the feature
mode of ULTRA55 scanning electron microscope manu-
factured by CarlzeissSMTrecLMD, Germany. 100 fields of
view were scanned for each sample in the refining phase.
Each field was scanned for 0.25 mm2, which total area is
25 mm2, and the size, quantity, composition and morphol-
ogy of each inclusions are analyzed statistically.
In Figure 1a, because the temperature in the refining
process is above 1823 K, the liquid region (50 wt.%, 75 wt.%
and 100 wt.%) filled up by gray area is calculated by
FactSage 6.4 software. The inclusions’ average composition
moves toward the calculated high-melting-temperature
region as the reaction time increases, because the inclusions
evolve toward the periclasite phase (cubic crystalline MgO).
It is obvious in Figure 1b that the MgO content in the
inclusions continues to increase with reaction time, varying
from ∼18% at AOD reduction to ∼58% at LF departure. At
the same time, the Al2O3 content in the inclusions decreases
with increases in reaction time, varying from 75% at AOD
reduction to 19% at LF departure.
4 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017)

Table 3. Distribution of main elements in different inclusions and clusters in steel samples from mapping.

Typical Element
Combined
Smelting stage
map
photo Magnesium Aluminum Calcium Silicon Oxygen

AOD

reduction

AOD

reduction

AOD

tapping

AOD

tapping

LF

arrival

LF

21min

LF

35min

LF

55min

LF

departure
 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017) 5

(a) (b)

(c) (d)
Fig. 1. Nature of each type of inclusion at the different refining stage: (a) composition of oxide inclusions at different liquid phase
region of 50%, 75% and 100% in MgO–Al2O3–CaO (SiO2) system, (b) monoxide content changed in inclusions with reaction time,
(c) number density (ND) of different types of inclusions and (d) total area of different types of inclusions in refining stage.

It can be seen from Figure 1c that a large amount of
Al2O3, MgO–Al2O3, and MgO–Al2O3–CaO–SiO2 deoxida-
tion products were formed by Si–Al complex deoxygen-
ation in the AOD process. In combination with Figure 1d, it
can be found that the equivalent areas of Al2O3, MgO–
Al2O3, and MgO inclusions were very small, whereas the
liquid MgO–Al2O3–CaO–SiO2 inclusions have a larger size
in which the total equivalent area reaches 2.52  104 mm2
per 25 mm2 (scanninging zone). When AOD tapping, with
the characterized slag-metal mixing, the solid inclusions
such as MgO · Al2O3, Al2O3, etc., were wrapped with liquid
MgO–Al2O3–CaO–SiO2 inclusions or slag globule. These
turned into larger inclusions. The typical morphology of
such inclusions is shown in Table 3.
With the refining carried out, this type of inclusion can
be floated quickly. As a result, the number and size are both
reduced in the early stage of LF refining. Compared with
the early stage of LF refining in Figure 1c and d, the size
and number of all types of inclusions in the AOD process
decreased after LF departure, while the number of newly
formed MgO increased continuously. Finally, the redox
reaction between Mg–O gradually became dominant until
LF departure. Throughout the course of LF refining, the
size of MgO inclusions is always smaller than other types of
inclusions, which proves that MgO-rich inclusion or pure
MgO particles, compared with MA spinel, were easier to
disperse in melts.
4 Evolution mechanisms of inclusions
containing pure MgO
4.1 Thermodynamic discussion of slag/steel reaction
For slag/steel reaction, the transformation process of the
inclusions consisted of two steps. (1) CaO and MgO in the
slags were reduced and entered the molten steel as Ca and
6 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017)
Mg; and (2) Ca and Mg in molten steel reacted with the
inclusions and entered the inclusions as CaO and MgO.
Both steps should be considered when investigating the
formation sequence of CaO and MgO in the inclusions.
From the perspective of thermodynamics, although
CaO is more difficult to reduce than MgO in step (1), CaO
in inclusions was more likely to form than MgO in step (2).
If slags/steel/inclusions reached a complete equilibrium,
no difference would exist in reduction or concentration
potential. The slag/steel oxidization–reduction reaction
was actually a process of Ca, Mg, and Al ions competing
to react with O ions. From the above, MgO content in
the inclusions always increased throughout refining,
indicating that the activity of Mg was very high in molten
steel. In order to verify the relationship of the activities of
the above elements, a thermodynamic equilibrium of
slag/steel/inclusion had to be established first.
Although the present metallurgical thermochemistry is
already well developed, several problems remain in the
calculation of slag-steel equilibrium. For example, the
Wagner model of interactive coefficients of multiple
systems, the most widely used, did not apply if the solute
concentration was high. Moreover, no reliable data (the
interaction parameter) for Ca and Mg in high-alloy steels
has yet been presented in the literature.
FactSage thermodynamic software [16] using the new-
est FACT oxide database (FToxid databases) [17–19] and
liquid steel database (FSstel databases) [20] could predict
the deoxidization equilibrium of molten steel very well,
especially for multicomponent alloys. For the deoxidization
phenomenon in liquid steel (FSstel databases), a new
Associate Model was used in simulation [20]. Detailed
information regarding the Associate Model and parameters
such as Ca, Mg, Al, Mn, and Si deoxidizers has been
reported by Jung et al. [20]. Based on the data in Tables 1
and 2, the activity calculations for Ca, Mg, and Al are
performed as shown in Figure 2. The activity of Mg is
always higher than that of Ca and Al after LF arrival. After
AOD tapping, the activities of Ca and Al decrease
throughout the LF refining process. This is because the
activity of Mg reaches a high level, the Mg–O reaction
remains dominant, and new MgO-based inclusions form
continuously. This illustrates well that MgO and MA spinel
formed before the CaO–Al2O3 inclusions. The higher
activity of Ca during AOD tapping is mainly caused by the
high activity of CaO in slag droplets and the reduction of
CaO by Al in good kinetic conditions, therefore causing the
rapid increase of Ca activity. However, the activity of Ca
drops below that of Mg in subsequent refining stages, as
illustrated in the following.
The activity of MgO and Al2O3 in top slag directly
affects the composition of inclusions. For 430 stainless
steel, the mole ratio of MgO to Al2O3 in the inclusions
linearly decreases by the decreasing activity ratio of MgO
to Al2O3 in top slag [2]. The rate of increase of Mg in molten
steel is determined by the activities of soluble oxygen and
MgO at the slag/metal interface, and hence by the slag
composition [4]. Very similar results were reported by Jiang
et al. [21] for Cr-containing high-strength structural steel.
Therefore, if using a high-basicity slag in which the activity
of MgO is greater than that of Al2O3, as well as the
Fig. 2. Activities of Ca, Mg, and Al in molten steel during
steel/slag reaction.
condition of CaO and MgO dual saturation, the MgO-rich
MA spinel solid solution is formed. Hence, CaO–SiO2–
MgO–Al2O3 systems are calculated with thermochemical
calculations at process temperatures using FactSage 6.4, as
shown in Figure 3, which provides information regarding
the secondary metallurgical ladle slag conditions.
From Figure 3, it can be understood that every slag
composition point throughout the refining process is in the
CaO and MgO dual-saturation condition. The character-
istics of the inclusions are consistent with the experimental
results, in that the MgO-rich MA spinel solid solutions
formed in the Fe–16Cr melts equilibrated with basic slags
highly saturated by CaO–MgO [2]. This was proposed to be
caused by the activity of MgO in MgO-saturated slags
reaching unity. With the increase of slag basicity, the
oxygen content at the slag/steel interface decreased and
MgO formed in the slag/steel interface reaction increased,
resulting in the increase of MgO content in inclusions.
The above discussion about slag/steel reactions is based
on CaO–MgO doubly saturated slag as a prerequisite.
Todoroki and Mizuno [12] studied the effects of CaO and
MgO unsaturated slag on the evolution of inclusions in Al
deoxidized 304 stainless steel. When the content of SiO2 in
slag is relatively high, more spinel is formed after Al
addition by preventing the excessive reduction of MgO in
the slag by Al, which prevents the further transformation
of MgO–Al2O3 to MgO and/or CaO–MgO–Al2O3. In view
of this, the effect of SiO2 on the composition of Al-
deoxidized stainless steel inclusions is determined by the
slag alkalinity.
When the slag basicity is relatively high in contrast to
other types of stainless steel (the slag basicity in this paper
is about 2.7), the activity of SiO2 in a CaO–SiO2–MgO–
Al2O3–F system is very low. SiO2 can only affect the
activity of CaO, while MgO and Al2O3 activity is not
affected. Thus, the reaction of MgO being reduced by Al
cannot be influenced, and the inclusions will eventually
change to MgO-riched MA spinel. When the slag basicity is
relatively lower, such as the basicity in Todoroki’s
experiments [12] (about 1.6), the activity of SiO2 can
increase accordingly. Meanwhile, the activity of CaO and
 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017) 7

MgO decrease owing to the formation of Ca2SiO4 and

Mg2SiO4, which prevents the further transformation of
MgO–Al2O3 to MgO and/or CaO–MgO–Al2O3. Thus
indicates that the conditions for the formation of MgO-
riched MA spinel require that MgO in slag reach a saturated
state, and that the slag has a certain alkaline to restrain the
reaction between SiO2 and MgO. Through the Equilib
Module in FactSage 6.4, the equilibrium compositions of
molten steels with compositions listed in Tables 1 and 2
were calculated in order to further analyze the influence on
molten steel composition if composition changes of CaO–
MgO doubly saturated slag occurred during refining. As
presented in Figure 4, the Associate Model assumes that Ca,
Mg, Al, O, and other elements in molten steel exist both as
atoms and complexes, such as Ca*O, Mg*O, Al*O, Al2*O,
and so on. In this Associate Model, no oxide molecules are
assumed to exist and the complexes are distributed evenly in
molten steel. The measured results indicate the elemental
content of Ca, Mg, and O, or the content of Ca and Mg
Fig. 3. CaO–SiO2–Al2O3 with 10%MgO phase diagram of Mg
included not only in atoms in solid solution state but also in
solubility at 1823 K.
oxide molecules, and a certain distribution difference in oxide
concentration is shown. Thus, the calculated result is
generally expected to be somewhat higher than that actually
measured.
The element of Ca in Figure 4 is special because its
activity is inhibited under higher oxygen potentials during
the refining stage, as shown in Figure 5. Thus, Ca mainly
exists in molten steel as part of solid solutions. With the
decrease of temperature during the sampling process, the
content of dissolved oxygen decreased dramatically.
Therefore, the activity of Ca increased dramatically.
Because the cohesion capability between Ca and O is
the strongest, the measured content of total Ca was higher
than that calculated. Above all, element changes in molten
steel were shown to affect inclusion composition. Based on
the measured composition of slags and molten steel, the
elemental content of Ca, Mg, and Al calculated through
Associate Model approached the actual values at the
smelting temperature. Therefore, the evolution of inclusion Fig. 4. Comparison analysis between detection component and
compositions could be illustrated more reasonably from the equilibrium composition.
perspective of thermodynamics.

4.2 Illustration of evolution of MgO-based inclusions
during steel/slag reaction
From the above evolution characteristics of inclusion
composition and thermodynamic analysis, Mg–O reaction
was always dominant. On one hand, Mg continued to
replace Al2O3 in the MgO-rich MA spinel; on the other
hand, new MgO phase continued to form. MA spinel did
not further transform into the CaO–Al2O3–MgO system.
This was mainly because the Ca atoms from the slag/steel
reaction reacted with the initially generated liquid Al2O3–
CaO–SiO2 and replaced the SiO2. Therefore, the Ca atoms
were inhibited from replacing MgO in MA spinel. In
addition, Si–Al complex deoxidization and relatively low-
basicity slags were adopted in the AOD refining process.
The [O] concentration at the slag/steel interface was higher
than that in the Al-killed molten steel refined by high-
basicity slags. In this situation, the activity of Ca was
inhibited and Ca was prevented from replacing MgO in MA
spinel. Based on the preceding analysis, the formation
mechanism of the inclusions containing MgO cores in
commercial stainless steelmaking processes is schematical-
ly described in Figure 6.
For high-alloy melts containing Cr, it was considered in
Associate Model that oxygen not only dissolved in molten
steel as atoms to form complexes with Ca, Mg, Al, and Si at
high temperatures, but also formed Cr*O and Cr2*O with
Cr. This also contributes to the higher total oxygen content
of stainless steel melts than that in low-alloy steel. For 2205
stainless steel, the content of Cr reaches 23%, and low-Al
deoxidization is adopted for a total oxygen content above
0.002%. In this condition, the activity of Ca is strongly
inhibited and always lower than that of Mg. Meanwhile,
the oxygen content in the molten steel was determined by
the Mg–O reaction, which was always dominant. This is the
primary cause of formation of MgO-cored inclusions. In
combination with Table 3, it can be concluded that the
outer constituents of MgO-cored inclusions are transformed
8 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017)
from the high-melting-temperature CaO–Al2O3 system into
the liquid low-melting-temperature CaO–Al2O3 system
during the later refining stages until LF departure. In the
process of transfer from tundish to mold, these systems would
collide with each other and aggregate into large inclusions
much more easily. If the total oxygen content was controlled
to approximately 0.002% to inhibit the activity of Ca and
make MgO-spinel dominant in the outer layer of MgO
inclusions, it would be more helpful to the dispersive
distribution of small, pure MgO inclusions.
4.3 Model establishment on evolution kinetics of
MgO-based inclusions
Although the evolution of MgO core inclusions was
discussed thermodynamically and described schematically,
the phenomenon of MgO cores remaining unchanged to
high-melting-point MgO–Al2O3 systems, before trans-
forming to lower-melting-temperature CaO–Al2O3–MgO
systems under the conditions of Al and Ca in steel, has not
been discussed. Therefore, further understanding on the
evolution kinetics of inclusions was necessary to determine
the limited steps. As a result, a model was established to
help understand the evolution kinetics of inclusions.
Before the model was established, several assumptions
and pre-requisitions were given for convenience of discus-
sion, listed as follows:
– Solid inclusions were considered as spherical particles,
uniformly distributed in the melts. The chance of each
solid inclusion changing into MgO–Al2O3 system inclu-
sions was equal.
– During inclusion/steel reaction, the solid inclusion
changed uniformly in every direction and maintained
spherical symmetry.
– A rectangular coordinate system was set with the origin
at the center of the solid inclusion core; the X-axis
represents distance while the Y-axis represents the
content of the inclusion component.
– Spinel formed by the change of MgO ! MgO–Al2O3 is
marked as MgO-spinel.
As the observed MgO core inclusions were formed by
Mg–O reactions, and the composition change of structure
over time followed the order of MgO ! MgO-spinel
layer ! CaO–Al2O3 layer, and because the MgO-spinel
layer ! CaO–Al2O3 layer transition has been discussed in
detail [13,22]. In order for convenience in this discussion,
only the modification mechanism of the MgO (periclase)
into inclusions are described by employing the intermedi-
ate layer concept, as schematically expressed in Figure 7.
The reaction steps are given as follows:
– Al atoms diffuse from the bulk into the MgO/molten
steel interface.
– Reaction of Al into Al3+ occurs at the steel/Al2O3
inclusion interface:
AlðlÞ ¼ Al3þ þ 3e : ð1Þ
– Al3+ diffuses through the intermediate layer with
equimolar vacancies diffused in the opposite direction.
Fig. 5. Activities of Ca and Mg in 2205 stainless steel melt in
equilibrium with slag saturated with MgO and CaO at 1823 K.
– Reaction (2) between solid MgO and Al3+ occurs at the
surface of MgO inclusions. As a result, a thin layer of
MgO-spinel layer is formed around the MgO inclusion.
2Al3þ  3Mg2þ þ 4MgO ¼ MgO⋅Al2 O3 : ð2Þ
2Al3þ þ ½MgO6 10 ¼ MgO⋅Al2 O3 þ 2O2 : ð3Þ
– Al3+ diffuses through the newly formed thin MgO-spinel
layer and reaches the new reaction interface of
MgO/MgO-spinel. Reactions (2) and (3) continue.
– With increases in the thickness of the newly formed layer,
the reaction rate of equations (2) and (3) are decreased.
The preceding mechanism of inclusion modification is
based not only on crystal (and molecular) chemistry, as
shown in Pauling’s integrated works, but also on the
ionic/covalent characteristics of the interionic bonds in the
solid (or liquid) oxide systems [22–24]. It has also been
suggested that the crystallization of the MA spinel phase in
glass-ceramics containing MgO and Al2O3 would occur
from the reaction between Mg2+, which occupies the
octahedral site, and Al3+ by employing Fourier-transform
infrared, X-ray diffraction, and nuclear magnetic resonance
analyses [25,26].
In view of kinetics, the oxidation rate of Al atoms to
Al3+ at the metal/intermediate layer interface (Eq. (1)) as
well as the diffusion rate of Al3+ through this layer would
exceed that of [MgO6]-octahedral units, or the diffusion
rate of Mg2+, in the boundary layer of the inclusion side.
This agrees qualitatively with the formation kinetics of the
MgO-spinel phase from the reaction between MgO and Al
during the oxidation of the Al–Mg alloys at high temper-
atures suggested by Zayan et al. [27]. They proposed that
the diffusion of Mg2+ in MgO-spinel solid solutions was a
rate-controlling step by employing surface analysis tech-
niques, such as X-ray photoelectron spectroscopy and
Auger electron spectroscopy as well as SEM and
transmission electron microscopy. Therefore, the modifi-
cation reaction, or the transformation from MgO periclase
 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017)
Fig. 6. Schematic of the formation mechanism of the inclusions
containing pure MgO during Fe-23% Cr-5% Ni-3% Mo high-
alloyed stainless steel manufacturing processes.
to MA spinel-type inclusions in molten steel equilibrated
with high-basicity slags, could be assumed to occur at the
intermediate layer/inclusion core interface and could be
controlled by the diffusion of Mg, i.e. [MgO6]-octahedral
units.
Through the industrial experiments in this paper, it
was demonstrated that, although the diffusion coefficients
of Mg and Ca were much lower than that of Al [22,27], the
concentration of Al was low enough in molten steel that
the potential energy of Al3+ was small, impeding diffusion
of Al into MgO cores to form MA-spinel. As a result, MgO-
spinel shells only formed at the MgO/metal interface; it
was energetically unfavorable to move the MgO-spinel/
MgO layer closer to the MgO core. Meanwhile, the
diffusion rate of Mg2+ in the generated MgO layer was
3.02  1016 m2/s, so that the diffusion of Mg2+ in MgO
core would be the rate-limited step, causing difficulty in
moving the MgO/MgO-spinel layer toward the MgO-
spinel layer. The contact angle (u) between the Fe–Cr
melt and pure Al2O3 is ∼90° and the work of adhesion
(WA) is ∼1000 mJ/m2, while u between Fe–Cr and pure
MgO is ∼125° and WA is ∼425 mJ/m2 at 1923 K under an
Ar atmosphere [28]. These physical properties indicate
that the wettability of MgO by 2205 stainless steel is
relatively suffused. Hence, the dispersion tendency of the
MgO-spinel inclusions would create good dynamic con-
ditions for the precipitation of inclusions with MgO cores.
9
Fig. 7. Schematic of MgO changing into MgO-spinel.
5 Conclusions
A plant trial of 2205 stainless steel production was
performed, and the characteristics of inclusion formation
during AOD/LF refining were investigated. Thermody-
namic equilibria among Mg, Ca, Al, and O, as well as MgO-
spinel and pure MgO formation with steel/slag reactions,
were studied to understand the fundamentals of inclusion
modification. Furthermore, the change mechanisms of
MgO cores and MgO-spinel precipitation were discussed.
The following conclusions were obtained:
– The composition of oxide inclusions changed along the
path of MgO–Al2O3 ! MgO-spinel ! CaO–Al2O3–MgO–
(SiO2) during AOD/LF refining. MgO-spinel and
CaO–Al2O3–MgO–(SiO2) were characterized by pure
MgO cores surrounded by high-melting-temperature
MgO-spinel outer surface layers or relatively low-melting-
temperature CaO–Al2O3 systems.
– The MgO-rich MA spinel solid solutions formed in the
steel melts equilibrated with slags in which CaO and
MgO were dually saturated. MgO provided sufficient Mg
to the steel melts. As the Mg–O deoxidization reaction
approached equilibrium, the newly generated pure MgO
could exist stably. Meanwhile, the dimension of MgO
particles increased. It indicated that MgO particles were
liable to form in 2205 stainless steel melts equilibrated
with CaO and MgO saturated slags.
– Through Associate Model in FactSage 6.4, the activity
changes of Ca, Mg, and Al during the refining process
were calculated based on the reaction between slag and
steel. It was found that activity of Mg was higher than
those of Al and Ca, such that the Mg–O reaction was
dominant throughout refining. Compared with Al2O3,
the contact angle between Fe–Cr melts and pure MgO is
greater, while the adhesion work is relatively lower.
Therefore, pure MgO more easily forms in molten steel
under conditions of low Al contents.
10 Z. Pang et al.: Metall. Res. Technol. 114, 211 (2017)
– Because of the low concentration of Al in molten steel,
the low potential energy of Al3+ out of the boundary, and
the extremely low diffusion rate of Mg2+ in the MgO core,
almost all inclusions had MgO cores with thin MgO-
spinel shells. In addition, a mechanistic illustration of
inclusion formation was given based on the un-reacted
core model.
– Although the content of CaO in the LF slag reached
saturation, the activity of Ca was strongly inhibited
because of the high activity of oxygen in steel with low Al
concentration. Therefore, it was difficult to transform
the MgO-spinel layer to liquid CaO–Al2O3 system
completely.
The authors are grateful for support from the National Science
Foundation China (NSFC 51334001 and 51574021), Beijing Key
Laboratory of Special Melting and Preparation of High-end
Metals (SMPHM) and the High Quality steel Consortium
(HQSC) at the School of Metallurgical and Ecological Engineer-
ing at University of Science and Technology Beijing (USTB),
China.
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