J. Iron Steel Res. Int.

(2022) 29:34–43
https://doi.org/10.1007/s42243-021-00637-8 (0123456789().,-volV)(0123456789().
,- volV)

ORIGINAL PAPER

Analysis on clogging of submerged entry nozzle in continuous casting

of high strength steel with rare earth
Wei Liang1 • Jing Li1 • Bin Lu2 • Jian-guo Zhi2 • Shuai Zhang2 • Yang Liu1

Received: 6 January 2021 / Revised: 8 April 2021 / Accepted: 11 April 2021 / Published online: 3 August 2021
Ó China Iron and Steel Research Institute Group 2021

Abstract
The type of inclusions in tundish steel and the formation mechanism of the submerged entry nozzle (SEN) clogging in the
continuous casting of the rare earth (RE) high strength steel without calcium treatment were studied based on the plant
trials and thermodynamic calculation. It was found that Ce2O3 and CeAlO3 in tundish molten steel were transformed into
Ce2O2S ? CaO–Al2O3 with the size of 2–3 lm during cooling. When the flow velocity of molten steel on surface of the
SEN was slow due to the boundary layer effect, Ce2O3 inclusion in molten steel reacted with Al2O3 in the SEN refractory
to form CeAlO3. With the continuous erosion of molten steel and reaction, the compositions of CeAlO3, Al2O3 and CaO
were aggregated, and the clogging layers with different zones were formed on surface of the SEN. Meanwhile, a small
amount of molten steel remaining in the arc zone and corner zone of the SEN formed solidified steel. When calcium
treatment is canceled, the reaction probability between inclusions in molten steel and refractory should be reduced by
improving the material and shape of the SEN.

Keywords Rare earth inclusion  Tundish  Submerged entry nozzle  Clogging  Thermodynamic calculation

1 Introduction To solve the SEN clogging problem, researchers studied

the aspects of improving the SEN material, optimizing the
The quality and properties of steel are directly affected by SEN design, adopting calcium treatment and argon blow-
the cleanliness of molten steel. In the continuous casting ing technology. The corresponding control principles are
system, casting protection measures are usually taken to avoiding the reaction between molten steel and refractory
prevent the reoxidation of molten steel [1, 2]. The sub- materials, reducing the residence time of molten steel in the
merged entry nozzle (SEN) is made of refractory material, inner wall of the SEN, modifying inclusions, promoting the
connecting tundish and mold to protect the smooth casting floating removal of inclusions and reaction products
of molten steel. During the casting process, the SEN is [6–12]. At present, calcium treatment and argon blowing
continuously eroded by the high-speed flow of molten technology are widely used to alleviate the SEN clogging.
steel. At the same time, the high melting point inclusions, In recent years, the rare earth (RE) was usually added as an
reoxidation products and reaction products between molten alloying element into molten steel. The experimental results
steel and refractory materials are gathered on the inner wall showed that the RE can purify molten steel and modify
of the SEN, resulting in clogging, which will block the inclusions and micro-alloy in steel [13–17]. The appropriate
SEN in serious cases [3–5]. amount of Ce is added in steel can affect the microstructure
and grain size of heat-affected zone (HAZ) by controlling the
formation of inclusions based on RE oxide metallurgy
technology, which is beneficial to improve the welding
& Jing Li
[email protected] toughness of steel plate [18, 19]. A large number of fine and
dispersed RE inclusions in steel can play a strong pinning
1
State Key Laboratory of Advanced Metallurgy, University of effect on grain boundaries [20, 21]. In the practical produc-
Science and Technology Beijing, Beijing 100083, China tion, calcium aluminate formed in molten steel will be
2
Inner Mongolia Baotou Steel Union Co., Ltd., wrapped in the periphery of RE inclusions after calcium
Baotou 014010, Inner Mongolia, China

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Analysis on clogging of submerged entry nozzle in continuous casting of high strength steel... 35

treatment during the Ruhrstahl Heraeus (RH) refining, Table 1 Main compositions of SEN (wt.%)
resulting in the size of inclusions becoming larger, which is Al2O3 SiO2 TiO2 Fe2O3 CaO MgO Na2O B2O3 ZrO2
unfavorable for the realization of oxide metallurgy [22].
Therefore, whether calcium treatment is carried out during 82.1 6.8 1.2 0.3 0.1 0.2 1.1 2.3 5.8
the RH refining not only affects the SEN clogging, but also
affects the type and size of RE inclusions in steel. Also, the
production cost can be reduced by canceling calcium treat- and H), high-frequency infrared carbon sulfur analyzer (de-
ment during the RH refining. termination of C and S), inductively coupled plasma mass
For the RE steel without calcium treatment during the spectrometer (determination of Ce, Ca and Mg) and direct
RH refining, the types of inclusions in tundish steel and the reading spectrometer (determination of the others). The con-
compositions of SEN clogging were studied in this paper. tents of these compositions were measured three times with the
The formation mechanism of the SEN clogging was instrument and the average value was taken. Based on the
explained by analyzing the effect of molten steel and compositions, the Scheil model in Thermo-Calc software was
inclusions on the SEN, which provided the research basis used to calculate the solidus–liquidus temperature of the steel,
for improving the SEN clogging, reducing production cost and the FactPS, FToxid and FSstel databases in FactSage 8.0
and optimizing welding toughness. were selected to calculate the precipitation temperature and
content of different inclusions in molten steel. Furthermore, the
effect of different Ce contents on the precipitation and trans-
2 Experimental formation of inclusions in molten steel at 1600 °C is calculated
by FactSage 8.0. The sample was taken from 1/4 of the diam-
2.1 Materials eter of the steel using wire cutting machine and the sample size
was 10 mm  10 mm  10 mm. After grinding and polish-
The plant trials of Q690D high strength steel containing Ce ing, the inclusions in the sample were observed and analyzed
were carried out. The production process is shown in using a scanning electron microscope (SEM)–energy disper-
Fig. 1. The molten iron in the blast furnace (BF) was sive spectrometer (EDS). Table 2 shows the main chemical
pretreated and mixed into the 210 t basic oxygen furnace compositions of Q690D tundish steel. The contents of Ce, O
(BOF) for smelting. After tapping, the molten steel was and S was 0.0028%, 0.0012% and 0.0014%, respectively.
successively transported to ladle furnace (LF) station and The angle grinder was used to take samples at the three
RH vacuum refining furnace station for refining. Then, the different positions (the center of straight area, arc area and
ladle with molten steel was lifted to the continuous casting corner area) of the SEN, and the samples were washed with
(CC) system, which includes tundish, mold and caster. anhydrous ethanol and then dried. As shown in Fig. 2, the
120 kg Ce–Fe alloy (Ce C 10% ± 1%, O B 0.0100%, Fe samples were fixed with the mounting material and marked
balance) was added during the RH refining process without as sample 1, sample 2 and sample 3, which are located in
calcium treatment. The SEN was clogging during the the straight area, arc area and corner area of the SEN,
casting process, the staff replaced the SEN to avoid the respectively. Due to the high vibration frequency of the
SEN blocking affecting production. angle grinder in the sampling process, a small part of
Through field investigation, the molten steel in the tundish clogging and solidified steel on surface of the SEN fell off.
and the SEN was sampled. The main compositions of SEN Therefore, there were some mounting materials between
provided by the manufacturer are shown in Table 1. It can be the clogging and the inner wall of the SEN. The samples
seen that the SEN was mainly composed of Al2O3 (82.1%). were ground, polished, and sprayed with gold after drying.
Besides, the surface porosity of the SEN was 15.19%. The clogging area and solidified steel area on the inner wall
of the SEN were observed using the optical microscope
2.2 Methods (OM). The morphology and compositions of the clogging
were further observed and analyzed using SEM–EDS.
The compositions of tundish steel were determined using the
oxygen and nitrogen hydrogen analyzer (determination of O, N
3 Results and discussion

3.1 Morphology and types of inclusions

in tundish steel

The inclusions in tundish steel were mainly complex

Fig. 1 Production process of Q690D high strength steel inclusions, as shown in Fig. 3, which were spherical with

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Table 2 Main chemical compositions of Q690D tundish steel (wt.%)

C Mn Si P Cr Mo Ti Al Ce Ca Mg O S N

0.1360 1.530 0.250 0.016 0.310 0.180 0.014 0.028 0.0028 \ 0.0005 \ 0.0005 0.0012 0.0014 0.0037

Fig. 2 Sampling position and observation direction of SEN

the size of 2–3 lm. The outer layer of the inclusions was clogging and solidified steel in turn. The area of clogging
light gray and consisted of CaO–Al2O3 and a small amount was less, and the area of solidified steel was more in
of Ce. The inner layer of the inclusions was bright white sample 3 with the particularity of position. The reason of
and consisted of Ce–S. The area of Ce–S was larger. steel solidification is that the slow flow velocity of molten
Furthermore, the bright white area of the inclusions was steel in the two areas. Moreover, the rough surface of the
scanned by selective scanning, and the results are shown in SEN and clogging increases the contact area with molten
Fig. 4. The statistical results of elements distribution in the steel, which accelerates the heat dissipation and causes
selected area are shown in Table 3. solidification of molten steel.
Element O was found in the bright white area of the The clogging on surface of the SEN in sample 1 was
inclusions based on Fig. 4 and Table 3, and the content observed using SEM. As shown in Fig. 6, the clogging can
accounted for 24%. It is considered that the part is com- be roughly divided into zone I, zone II and zone III. Zone I
posed of Ce–O–S. Therefore, it can be determined that the was the closest to the SEN and can be considered as the
typical inclusions in tundish steel consist of Ce–O–S and first reaction zone. Zone II was located in the middle of
CaO–Al2O3. zone I and zone III, which was considered as the second
The melting points of Ce–O–S and Ce–S are both high reaction zone. Zone III was located in the outer layer,
based on Table 4 [23], and they can directly form inclu- which was considered as the third reaction zone. There
sions in molten steel. The melting point of CaO–Al2O3 is were holes in zone I, zone II and zone III, and the SEN
relatively low [24], so it wraps on surface of the Ce–O–S refractory can be seen inside the holes. It indicates that the
easily and forms the complex inclusions. chemical reaction and corrosion of refractory occur when
the molten steel contacts with the SEN, resulting in the
3.2 Morphology and compositions of SEN decrease in the stability of refractory and the increase in the
clogging thickness of clogging layer.
Table 5 shows the results of EDS analysis in different
Three different positions of the SEN were observed under zones of the SEN. The results showed that position 1 was
OM. Figure 5a, b and c shows the observation of sample 1, located in zone II, and it consisted of Ce–Al–O and CaO–
which were composed of the SEN and clogging. There Al2O3. Position 2 was located in zone I and consisted of
were a certain number and area of holes in the clogging. It MgO–Al2O3. Position 3 was located in zone III and con-
may be that the clogging fell off in the grinding process, or sisted of Ce–Al–O and a small amount of CaO. Positions 4,
the clogging has loose characteristics and poor 5 and 7 were all located in zone II, they belonged to dif-
compactness. ferent phases. Position 4 was composed of Ce–Al–O and
Figure 5d–f and g, h shows the observation of samples 2 CaO–Al2O3, position 5 was composed of CaO–Al2O3 and
and 3, respectively. They were composed of the SEN, FeO, position 6 was composed of CaO–Al2O3, and position

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Analysis on clogging of submerged entry nozzle in continuous casting of high strength steel... 37

Fig. 3 EDS results and backscattered electron (BSE) images of typical inclusions in tundish steel. a–c Element mappings of inclusions; d–
h typical inclusions

7 was composed of Ce–Al–O and CaO–Al2O3. The atomic 3.3 Formation mechanism of SEN clogging
percentage of Ce in position 7 was higher than that in
position 4. The area of phase composed of Ce–Al–O and Based on the thermodynamic calculation of the inclusions
CaO–Al2O3 was the largest in zone II. According to the transformation process in tundish molten steel, the type of
compositions of different phases in zone I, zone II and zone inclusions passing through the SEN was determined com-
III, the material compositions in the three reaction zones bined with the actual observation and analysis results,
are MgO–Al2O3 ? Ce–Al–O ? CaO–Al2O3 ? Ce–Al– which lays a foundation for clarifying the formation
O ? CaO  MgO–Al2O3 was the closest to inner wall of the mechanism of SEN clogging.
SEN. It is considered that MgO mainly comes from the As shown in Fig. 8a, the inclusions in tundish molten
SEN. steel were Ce2O3 and CeAlO3 at 1600 °C. The content of
The SEM–EDS analysis results of samples 2 and 3 Ce2O3 decreased, while the content of CeAlO3 increased
are shown in Fig. 7. There were clogging on the surface with the decrease in temperature. When the temperature
of the steel, and in Fig. 7a and b, the compositions from was 1480 °C, Ce2O2S was formed and increased. The
left to right were Fe ? FeO ? Ce–Al–O ? CaO ? content of CeAlO3 reached the maximum at 1460 °C,
FeO ? CaO–Al2O3 and Fe ? Ce–Al–O ? CaO ? while Ce2O3 disappeared. After that, the content of Ce2O2S
FeO ? Fe, respectively. Combined with Fig. 6 and increased but the content of CeAlO3 decreased gradually.
Table 5, it can be determined that the clogging on the CeAlO3 disappeared at 1260 °C, but Ce2O2S still existed.
surface of the steel (Fig. 7) is located in zone III. There The calculated results are consistent with the results of Ce–
was no calcium treatment in the refining process, CaO in O–S observed in tundish steel. Combined with EDS anal-
the inclusions and clogging mainly comes from the slag ysis results, the main component of inclusions is Ce2O2S,
in the smelting process, and the others come from the which is formed with the cooling transformation of molten
SEN refractory. steel. The liquidus and solidus temperatures of Q690D

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Fig. 4 EDS results of typical inclusions in tundish steel. a, b EDS spectrums of inclusions; c–f typical inclusions

Table 3 Percentage of atoms in different positions of typical inclu- temperature of molten steel in tundish was 1530–1550 °C.
sions (at.%) The inclusions in molten steel are Ce2O3 and CeAlO3
Position Ce O S Fe Ca Al according to the calculation results.
In Fig. 8b, the precipitation of inclusions with different
1 44.50 24.14 19.65 10.07 0.65 – Ce contents in molten steel at 1600 °C was calculated.
2 32.33 23.47 14.66 24.03 2.84 2.67 CeAlO3 was gradually formed in molten steel with the
3 40.12 26.47 20.32 10.36 1.99 0.74 increase in Ce content, which was the result of the reaction
4 34.05 21.15 16.63 22.85 3.76 – between Ce and Al2O3 [26]. The content of CeAlO3
5 40.97 24.06 18.24 15.43 1.30 – reached the maximum when Ce was 0.0016%. With the
6 46.93 23.82 20.56 7.27 1.42 – increase in Ce content, the RE inclusions changed from
CeAlO3 to Ce2O3. CeAlO3 were completely transformed
into Ce2O3 when Ce was 0.034%. Then, the content of
Table 4 Melting points of different types of inclusions (°C) [23] Ce2O3 began to decrease and gradually changed into Ce2-
Ce2O3 Ce2O2S CeS Ce2S3 Ce3S4 O2S inclusion. It can be seen that the inclusions are mod-
ified by Ce in molten steel, and the change of inclusions is
1690 1950 2450 2149 2080 ± 30
as follows: Al2O3 ? CeAlO3 ? Ce2O3 ? Ce2O2S. When
Ce is 0.0028%, the inclusions in molten steel are Ce2O3
and CeAlO3, which are consistent with the calculation
tundish steel were 1515 and 1460 °C, respectively results in Fig. 8a. When Ce2O3 contacts with Al2O3, the
(Fig. 8a). The superheat degree of molten steel in tundish is reaction equation will be as follows [27]:
15–35 °C [25], and it can be considered that the

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Analysis on clogging of submerged entry nozzle in continuous casting of high strength steel... 39

Fig. 5 OM images of clogging and solidified steel on surface of SEN. a–c Different positions of sample 1; d–f different positions of sample 2; g,
h different positions of sample 3

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40 W. Liang et al.

Fig. 6 BSE images of different areas of clogging in sample 1

Table 5 Percentage of atoms in different zones of clogging in sample Figure 9 shows the schematic diagram of the SEN clogging
1 (at.%) formation.
Element Ce O Al Ca Mg Fe The clogging process of the SEN can be divided into
four steps (Fig. 9). Firstly, when the molten steel in tundish
Area 1 3.59 44.27 20.65 9.13 – – flows through the SEN, the inclusion particles are sus-
Area 2 – 54.42 30.58 – 15 – pended in the molten steel. Secondly, because the interface
Area 3 24.01 46.77 23.73 5.49 – 0.74 energy between inclusions and molten steel is higher than
Area 4 9.08 47.74 28.96 13.11 – – that between inclusions and the SEN, and the surface of the
Area 5 – 61.02 9.12 0.94 – 28.74 SEN is rough, some inclusions with high melting point
Area 6 – 59.06 18.88 20.92 – 1.00 adhere to surface of the SEN. Ce2O3 inclusion will react
Area 7 16.85 47.33 25.25 8.09 1.91 with Al2O3 in the SEN refractory, and the formula is shown
in Eq. (1). Then, the inclusion particles are gathered on the
surface of the SEN, and the chemical reaction is also
continuously carried out. The initial clogging layer is
1=2Ce2 O3 ðs) þ 1=2Al2 O3 ðsÞ ¼ CeAlO3 formed and the SEN refractory is continuously eroded by
ð1Þ
DGh ¼ 24; 000  10T the reaction and molten steel. Finally, the reaction product
CeAlO3 and other inclusions are continuously gathered in
where DGh is standard Gibbs free energy, J/mol; and T is
the clogging layer due to the low interfacial energy
Kelvin temperature, K.
between inclusions, so the thickness of the clogging layer
Based on the analysis results of clogging in Table 5 and
increases obviously. In addition to the reaction products, a
Fig. 8, it can be considered that Ce–Al–O is mainly
part of CeAlO3 in the clogging comes from molten steel.
CeAlO3, which is the reaction product of Ce2O3 and Al2O3.

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Analysis on clogging of submerged entry nozzle in continuous casting of high strength steel... 41

Fig. 7 BSE images and EDS results of clogging and solidified steel in samples 2 and 3. a, b Line scan of solidified steel and clogging; c, d area
scan of clogging

3.4 Prospects for preventing clogging in SEN products will cause the SEN erosion and clogging. It will
hinder the flow of molten steel, resulting in the aggravation
Based on the research results, when inclusions in molten of clogging, and the solidified steel forms easily in the arc
steel react with the SEN, molten steel and the reaction and corner area of the SEN. Moreover, canceling calcium

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Fig. 8 Property diagram of inclusions precipitation of steel in tundish. a Different temperatures; b different Ce contents

Fig. 9 Schematic diagram of clogging formation in SEN

treatment and playing the role of RE oxide metallurgy are 4 Conclusions

important measures to reduce production costs and
improve steel properties. Therefore, the SEN material and 1. The typical inclusions in tundish steel were
shape should be improved to reduce the SEN clogging Ce2O2S ? CaO–Al2O3, which were spherical and
probability. small in size. Ce2O2S in inclusions was the product of
On the one hand, Ce2O3 inclusion is easy to react with the transformation of Ce2O3 and CeAlO3 in molten
Al2O3 in the SEN refractory, so the appropriate amount of steel during cooling.
Ce2O3 can be added to the SEN refractory to reduce the 2. The clogging on the surface of the SEN can be divided
chemical reaction. At the same time, the SEN clogging can into three zones, and the reactions of compositions were
be avoided by reducing the thermal conductivity and per- MgO–Al2O3 ? CeAlO3 ? CaO–Al2O3 ? CeAlO3 ? CaO.
meability of the SEN. With the influence of the SEN shape and clogging, the
On the other hand, molten steel and high melting point solidified steel was formed in the arc area and corner
inclusions are easy to stay and adhere to the inner wall of area. The main compositions of the clogging near the
the SEN. Adjusting the internal shape of the SEN to be solidified steel were CeAlO3 ? CaO.
cylindrical or threaded, reducing the roughness of the inner 3. The flow velocity of molten steel in tundish on the SEN
wall of the SEN, and increasing the inner diameter of the surface was slow, and Ce2O3 in molten steel reacted
lower part of the SEN can avoid the reaction and accu- with Al2O3 in the SEN refractory to form CeAlO3. The
mulation of inclusions. agglomeration of CeAlO3 with other inclusions resulted
in the formation of clogging layers with different reac-
tion zones.

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Analysis on clogging of submerged entry nozzle in continuous casting of high strength steel... 43

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