SEN clogging during continuous casting: mechanism and

countermeasure in chemistry aspect

Youn-Bae Kanga,b, Dong-Jun Leea, Yong-Min Choa, Joo-Hyeok Leec, and Jun Hyun
Kimd
a
Graduate Institute of Ferrous and Energy Materials Technology, Pohang University of Science and
Technology, Pohang, Republic of Korea
b
Department of Materials Science and Engineering, Pohang University of Science and Technology,
37673 Pohang, Republic of Korea
c
Technical Research Laboratories, POSCO, Pohang, Republic of Korea
d
Solution Centre, Chosun Refractories, Pohang, Republic of Korea

Key Words: Continuous casting; Nozzel clogging; SEN refractory; Carbothermic

reaction; Countermeasure; CO absorber; Oxynitride

Abstract
Continuous casting of liquid steel from tundish to mold is performed by flowing the
liquid steel through SEN. However, the inner hole of the SEN is often clogged, and
consequently, the casting process is interrupted. The clogging deposit also falls
off, enters into the liquid steel in the mold, and eventually appears on the surface of
the cast product. Suppressing nozzle clogging is therefore essential to increase
the productivity and quality of the cast product. While various origins have been
identified for causing nozzle clogging, the present study focuses on the reaction
chemistry-based aspect. The initiation of the clogging is due to an interfacial
reaction between the inner wall of the SEN and the liquid steel passing through the
SEN. In particular, the carbothermic reaction inside the SEN (SiO2(ref.) + 3C(ref.)
= 2CO(g) + SiC(s)) generates CO(g), which causes reoxidation of the liquid steel,
resulting in clog deposit formation. This initial clog deposit can be a subsequent
build-up site for inclusions in the liquid steel. Therefore, it is necessary to suppress
the reoxidation. In the present study, the fundamental reaction is discussed in view
of thermodynamics, a series of laboratory-scale experiments including in-situ gas
analysis in the emitted gas, and proposals to suppress the CO(g) generation.
Three approaches will be shown: 1) minimizing SiO2/C ingredients, 2) adding CO
absorbers, and 3) replacing SiO2/C ingredients with non-oxide type ingredients
(oxynitride-nitride mixture) in the SEN refractory. Significantly improved results
were obtained, in terms of suppressing clog deposit growth and casting plant trials.

Introduction
Continuous Casting (CC) is one of the necessary technologies to enable the massive
production of high-quality cast products. All the liquid steel refined in the secondary
refining process must pass a tundish to a casting mold by a Submerged-Entry Nozzle
(SEN). It has been a long-standing problem that the SEN often fails to deliver the
liquid steel to the mold by SEN clogging. There are several reasons for the
clogging: transport of oxides present in steel, air aspiration into the nozzle, chemical
reaction between nozzle refractory and steel, steel solidified in the nozzle, etc. [1].
SEN clogging is more problematic for the CC of Ultra-Low C steel (ULC) steel. This
 becomes even more severe when Ti exists in ULC steel (Ti-ULC) steel, such as
automotive steel [2]. The role of Ti in the cleanliness of Ti-ULC steel has been
recently discussed [3]. It has been recently an issue that chemical reactions
involving Ti in the liquid steel with SEN refractory material are the leading cause of
the initial stage of SEN clogging. Subsequent building up of suspending inclusions
on the initial clog deposit resulted in severe nozzle clogging [4,5]. The present
authors have reported that carbothermic reaction in the SEN refractory generates
CO(g), which then reoxidizes liquid steel. This reoxidation is more severe when Ti
exists in the steel. The reaction mechanism was recently elucidated by
thermodynamic analysis and a series of high-temperature experiments in the preset
authors' laboratory [6-12]. Based on the reaction mechanism, probable
countermeasures have been developed. This presentation introduces the reaction
mechanism and the countermeasures, in collaboration with industrial partners.

Thermodynamic analysis and experimental validation I: carbothermic

reaction
Most available SEN refractories contain SiO2 and C. These proceed with the
following carbothermic reaction at the casting temperature:

SiO2(s) + 3C(s) = SiC(s) + 2CO(g) (1)

The Gibbs energy change of Reaction (1) was negative at the casting temperature,
and most likely to happen out of other types of chemical reactions probable in SEN
refractory [13]. The reaction was validated by employing high-temperature
pyrolysis of various SEN refractories using an induction heating furnace and
Quadrupole Mass Spectrometer (QMS) to detect the gas species emitted from the
AGS
SEN refractories in situ. See [13] for the experimental
100
(a) 1600 details.
5
(b) Fig. 1 shows one of 60the (d) results of the pyrolysis

of4 AGS SEN refractory, which was composed by Al2O3,

40
Y28
Y32

Y28
Y32

20
SiO 2, C, etc. According to Reaction (1), only CO(g) is
75
Volume Fraction (%)

1200
Temperature ( C)

3 0
expected
(c)
to be detected by the QMS.
(e)
It was confirmed
20
Volume Fraction (%)

Volume Fraction (%)

50 Y
that CO(g) whose molecular mass is 28 was emitted
44
800
Y 40 Y 10 44
Y 15
when the refractory was heated.
32 Y 32
Y 28
25 400 Y Y
28 10 44
5 Y32
Y28
5
Fig. 1. Gas analysis result of AGS refractory: temperature profile of the
0 0
0 40 80 120 160
sample
0
during
20
the
40
pyrolysis
60
and
80
0
volume
80
fractions
100
of
120
four-different
140
0 gas
160
−1
Time (min) species of molecular
Time (min) mass (28, 32, 40, and 44 gTime
mol(min)
) [13].

Thermodynamic analysis and experimental validation II: reoxidation of

liquid steel and formation of FAT

Reaction (1) subsequently causes reoxidation of the liquid steel [3,6,7]:

CO(g) + Fe-Al-Ti = Al2O3(s) + FetO-Al2O3-TiOx(l) + 3C (2)

where FetO-Al2O3-TiOx(l) is a liquid oxide solution at the casting temperature [3,12].

The generated Al2O3(s) and/or FetO-Al2O3-TiOx(l) play a role in sticking suspending
inclusions in liquid steel [4]. FetO in the initial clog deposit is immediately reduced
by Al in liquid steel to form metallic Fe drops in the clog deposit [9]. The reaction
mechanism is shown in Fig. 2.

(a) (b) Proposed mechanism for Ti-ULC

clogging
SiO2 Fe ① SiO2 and C in refractory react to
form CO(g).
① CO(g) ② CO(g) moves through refractory
②
C ③ Ti pore.
③ CO(g) oxidizes Al/Ti/Fe
Al simultaneously.
④ C ④ FetO-Al2O3-TiOx(l) + Al2O3(s)
Al2O3
form and attach to the inner wall.
⑤
⑤ The liquid oxide containing FetO
FetO
C works as a binder to
-Al2O3-TiOx
Heat refractory/inclusion/liquid steel.
⑥ ⑥ FeO is gradually reduced by Al in
Al liquid steel or C in refractory,
forming reduced Fe and TiOx-
TiOx-Al2O3 Al2O3.
refractory steel

Fe reduced

Fig. 2. Reaction mechanism causing the early-stage clog deposit growth: (a) low C Al-killed steel [14] and
(b) ultra-low C Al-killed Ti-added steel [6].

It is clear that CO(g) from the carbothermic reaction plays a critical role in SEN
clogging. Therefore, it is necessary to suppress the CO(g) emission from the SEN
refractory.

Countermeasure I: minimizing SiO2/C ingredients

Several types of SEN refractories are available in the refractory market. Most of
the refractories consist of alumina, silica, carbon, and other ingredients such as lime,
zircon, etc. Depending on the composition of each refractory, the extent of the
carbothermic reaction would be different. In the present study, various SEN
refractories were employed: AGS, AG, CL, and CSG. All these are "oxide-base"
refractories, and their composition can be found elsewhere [13]. Fig. 3(a) shows
the QMS results of CO(g) fraction in the emitted gas during pyrolysis of each
refractory. The CO(g) fraction varies by the type of SEN refractory: AG emitted the
least CO(g) while AGS emitted the most CO(g). Total volume of CO(g) gas emitted
from 100 g of SEN refractory was compared with the following variable [13]:

𝑛!"#!(%) × 2 if 𝑛'(%) ⁄𝑛!"#!(%) > 3

Γ (mol per 100 gram SEN refractory) = 7 (3)
𝑛'(%) × !" if 𝑛'(%) ⁄𝑛!"#!(%) < 3

where G would represent the amount of available reactants for Reaction (1). Fig.
3(b) shows a favorable linear relationship between G and the volume of CO(g)
emitted. It is clear that more reactants for Reaction (1) cause more CO(g) emission,
which is then the source of the steel reoxidation via Reaction (2). This can cause
the initial clog deposit growth [6-9].
 Measured volume of CO(g) per gram SEN refractory (ml)
6

AGS 100
Volume fraction of CO(g) (%)

AGS
80

60 CSG
CSG

40 CL-adjusted CL
CL
2

20
AG

AG
0
0 0 0.1 0.2 0.3 0.4
80 100 120 140 160 (mol)
Time (min)
Fig. 3. Result of the carbothermic reactions in various SEN refractories: (a) estimated volume fraction of
CO(g) emitted by the pyrolysis reactions in four oxide-based SEN refractory samples,(b) relationship
between the measured volume of CO(g) and molar amount of reducible components in the oxide-based
refractories (AGS, AG, CL, and CSG) [13].

Countermeasure II: adding CO absorbers

From the previous countermeasure I, it is one way to select the appropriate SEN
which emits less CO(g). When a given SEN refractory should be used during CC,
it is the other way to capture the emitted CO(g) inside the SEN, before the CO(g)
propagates to the interface between the refractory and the liquid steel. Al4C3, B4C,
and CaC2 were considered as candidates for the CO absorber in the SEN refractory.
At high temperatures, these carbides react with CO(g) as:

Al4C3(s) + 6CO(g) = 2Al2O3(s) + 9C(s); DG°(4) (4)

B4C(s) + 6CO(g) = 2B2O3(l) + 7C(s); DG°(5) (5)
CaC2(s) + CO(g) = CaO(s) + 3C(s); DG°(6) (6)

A series of thermodynamic calculations were carried out to assess the possibility of

the above reactions. All the above carbides were able to capture CO(g) by the
above reactions. CaC2(s) was however hygroscopic, thereby rejected for further
consideration. Instead, Al was considered as another CO absorber by utilizing the
in-service formation of Al4C3(s) from Al and C in the refractory.

Ti-ULC steel sample (0.05Al-0.05Ti mass pct) was reacted with AG refractory with
or without CO absorbers at 1560 °C using a laboratory scale induction melting
furnace for 30 min. The specimen was quenched and examined by SEM-EDS for
its interface between the steel and the refractory. Fig. 4 shows the analyzed result
 when AGS refractory without CO absorber was used. The oxidized reaction
product (by Reaction (2)) is seen: Al2O3 and Al2O3-TiOx part. The latter is due to
the reduction of FetO in FetO-Al2O3-TiOx(l) [9].
(a) (b) Al (c) Ti
steel

(d) Fe (e) O

100 !m Refractory

Fig. 4. Reoxidation product between Ti-ULC steel and AGS refractory pellet: (a) SEM images at the
interface, (b)–(e) EDS mapping results for Al, Ti, Fe, and O, respectively [10].

80
T = 1560 C, AGS + CO abs./Ti-ULC steel, 30 min The thickness of the reaction product (dproduct) in
CO absorber various samples (Ti-ULC steel reacted with
Al4 C3
B4 C
AGS containing various CO absorbers) was
60 Al measured on SEM micrographs. Fig. 5 shows
the measured results. It was clearly seen that
(µm)

the addition of the CO absorber was effective in

decreasing the dproduct, and this means the
product

40

reoxidation by CO(g) emission was

suppressed.
20

Fig. 5. The average thickness of the reaction product layer

after the hot tests [10].
0
0 3 6 9
Mass pct, CO absorber

Countermeasure III: using oxynitride-nitride mixture in the SEN

refractory as non-oxide type SEN
Another way of suppressing the CO emission from SEN is the removal of the source
of CO emission. Instead of using oxide components, non-oxide type refractory
components may be used to fabricate SEN. In the present study, an oxynitride-
nitride mixture ALBN refractory was employed: AlN-AlON-BN ternary system without
any oxide and C. Fig. 6 shows the result of the pyrolysis of this refractory, which
was also carried out for the oxide-based refractories (Fig. 1). It was confirmed that
only N2(g) was emitted (N2(g) and O2(g) in the early stage of pyrolysis before 40 min
were due to the air which already existed in the measurement system). It is
therefore expected that using the "non-oxide" type SEN may be promising. Fig. 7
shows the hot test for the interfacial reaction between Ti-ULC steel and two
refractories (AGS (oxide-base) and ALBN (non-oxide base)). It is evident that
ALBN refractory suppressed the growth of the reaction product, which can be the
clog deposit.
 ALBN AGS (oxide-base) ALBN (non-oxide base)
16
12 Steel Steel
Y28
Y32

8
4
Al2O3-TiOx
0
1600
)
1

Temperature ( C)
1200 Al2O3
Flow rate (ml min

QN2 (g)
Al2O3
100 µm 100 µm
2 800 Refractory Refractory

1 400

QO2 (g) Fig. 7. Gas emitted by pyrolysis of ALBN SEN

0
0
0 40 80 120 160
refractory and flow rate of the emitted gases
Time (min) (N2(g) and O2(g)).
Fig. 6. Gas emitted by pyrolysis of ALBN SEN
refractory and flow rate of the emitted gases
(N2(g) and O2(g)) [13].

Summary and conclusion

SEN clogging during continuous casting of liquid steel is caused by the interfacial
chemical reaction between the SEN refractory and the liquid steel. The reaction
was initially caused by the internal carbothermic reaction in the SEN refractory. The
gas species emitted by the carbothermic reaction were confirmed by thermodynamic
analysis and in-situ pyrolysis gas analysis. It was found that CO(g) emission is the
leading source of the initial clog deposit growth. Three possible countermeasures
were proposed: 1) minimizing SiO2/C ingredients, 2) adding CO absorbers, and 3)
replacing SiO2/C ingredients with non-oxide type ingredients (oxynitride-nitride
mixture) in the SEN refractory. In particular, using an oxynitride-nitride mixture
(ALBN) refractory would open a new direction for the SEN clogging-free refractory
material development.

Acknowledgment
This research was financially supported by POSCO and Chosun Refractories, Ltd.

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