AISTech 2019 — Proceedings of the Iron & Steel Technology Conference

6–9 May 2019, Pittsburgh, Pa., USA

DOI 10.1000.377.218

Use of 6ynthetic 6lags to &ontrol the /evel of ,nclusions in 6teels

EA Vieira1, JR Oliveira1, FF Grillo1, AP Martins1, HCC Oliveira1, HS Furtado2
1
IFES Federal Institute of Espírito Santo
Av. Vitória, ES, Brasil, 29040-780
Phone:+55 27 3331 2278
Email: estefanovieira@ifes.edu.br
2
ArcelorMitall Tubarão
Av. Brg. Eduardo Gomes 526, Serra-ES, Brasil, 29160-904
Phone: +55 27 3348 1333
Email: henrique.furtado@arcelormittal.com.br

Keywords: Slag, Synthetic, Inclusion, Steel, Cleanness, ASCAT, Optical Microscopy

INTRODUCTION

The presence of inclusion in the steels plays a strong role in the steel product quality, so it is very important to have a deep
insight into the behavior of inclusions in the continuous casting. The studies of processes for searching steels with high level
of cleanliness are a concern that has being done around the world in steelmaking industry for many decades. All in all, the
phenomena that controls inclusions on steels are highly complex. It is well established that the during the deoxidation of
steels, the formation of non-metallic inclusions occurs, and the presence of them causes several problems both in the
production stages and in the final mechanical properties of the steel produced. Therefore, due to these problems, inclusions
should be removed from steels when possible [1]. According to the literature [1-3] the removal of inclusions occurs in three
stages. In the first one, called flotation, the inclusion is transported to the steel/slag boundary. In the second one, designed as
separation, occurs the rupture of the surface tension of the steel allowing the arrival of the inclusion to the slag. Finally, the
third and last step is the dissolution which is the most important, particularly for solid inclusions that have limited solubility
in slag and are therefore very sensitive to the physical and chemical characteristics, temperature gradients and the volume of
the slag. Results obtained by Choi et al [1] and used by Reis et al [4] highlight that the reduction of slag viscosity favors the
dissolution of alumina being its influence more important than the thermodynamic potential for dissolution as shown in
Figure 1.

Figure 1. Alumina dissolution on CaO–SiO2–Al2O3 slag system; a) as function of thermodynamic potential; b) as function
of viscosity [1].

© 2019 by the Association for Iron & Steel Technology. 2119

Therefore, as lower is the slag basicity, higher is its degree of polymerization so acid compounds such as SiO2 and Al2O3
contribute to higher viscosity values. On other hand, the high basicity in slags is due to the presence of basic compounds such
as CaO and MgO and them can drastically decrease viscosity due to their ionic behavior [5]. Based on this information, it
was concluded that to obtain a maximization of inclusion removal, especially those composed by alumina, it is necessary find
out mixtures with the lowest possible viscosity. Therefore, by using the ternary CaO-Al2O3-SiO2 diagram it was finding out
that slags with lower melting point tend to have lower viscosity considering a given fixed temperature. Figure 2 shows in
simplified form the example of two different slag compositions and which way forward in a hypothetical process aiming at
lowering the viscosity. In the examples given, it is noticed that to achieve this it would be necessary to add more alumina
and, also depending on the state CaO additions can be necessary, taking care to not to pick up a path of rise of the melting
point that can be leaded by an unsuitable choice of the CaO/Al2O3 ratio.

Figure 2. Schematic diagram showing how two paths of different slags could be changed to maximize inclusions removal.

The aim of this work was to reach methods to study inclusion removal from steels relating properties such as viscosity and
chemical composition of slags with their ability to remove inclusions from steels. Therefore, five slags were developed using
as reference the viscosity of the liquid phase as well as the percentage of the liquid phase. Slags were added over the melted
steel and the level of inclusions before and after the experiments were compared. The slags were also analyzed after the
experiments using x-ray diffraction to identify the formed phases. The results indicate that the slags tested can remove
inclusions. However, slag with high content of CaO has greater efficiency in inclusion removal.

EXPERIMENTAL

Materials
Figure 3 shows two singular micrographs of the steel in raw stage. The images were obtained for the same material and it is
noticed that the level inclusions change greatly from one microregion to another. Initially it was believed that the
characterization of a single sample would be able to define the initial inclusion level for the present study. However, the
results showed that each sample had its feature where inclusions levels ranged from 56 up to 729 inc/mm2. Thus, to obtain the
actual performance of the experiments, for each of them, inclusion levels were measured following the guidelines of the
standard (ASTM E45-13, 2017) [6].

Figure 3. Usual micrographs showing the level of inclusions in the steel, a) region with a large amount of inclusions 326
incmm2 and in b) region with low inclusions level 51 inc/mm2.

2120 © 2019 by the Association for Iron & Steel Technology.

For the present study, 0.3 kg of deoxidized steel was used for each experiment and Table 1 shows the chemical composition
of the steel.

Table 1. Chemical composition of steel used.

Fe C Si Mn P S
98.6 0.03 0.006 0.2 0.007 0.006

The slags were concepted based on patterns compositions found in the industrial processes of steelmaking. Thus, from these
compositions and with the aid of the FactSage® software 6.4 simulations were performed to evaluate the viscosity and the
initial liquid amount as a function of the binary basicity and the CaO/Al2O3 ratio. Figure 3a correlates binary basicity with the
viscosity of the liquid phase. It seems, that presence of MgO does not appear to significantly affect the viscosity of the slags
studied. In addition, when comparing Figure 4a with Figure 4b we find out that for a higher liquid fraction there is an
increase in the viscosity and formation of solid phases. Figure 3c correlates viscosity and the percentage of liquid phase with
the CaO/Al2O3 ratio. In this case the increase in Al2O3 enhance liquid phase and viscosity.

Figure 4. Viscosity and liquid fraction (a) viscosity as function binary basicity, (b) liquid fraction as function of binary
basicity, (c) viscosity and liquid fraction as function of CaO/Al2O3 ratio.

Thus, these results allowed to select slags with higher fraction of liquid phase and with the lower viscosity. The compositions
were formulated based on SiO2-CaO-Al2O3 system and other compounds aiming a maximum amount of liquid, minimum
viscosity, and a better efficiency for the fixation of inclusions in slags was expected. Table 2 shows the range of compositions
chosen as well as the calculated viscosities and the binary basicity index. In the simulations, slag was used with and without
the presence of MgO, high and low FeO. We can also see the fraction of liquid present for all thermodynamic simulations. As
reference for the simulations the temperature of 1600 OC was chosen.

© 2019 by the Association for Iron & Steel Technology. 2121

 Table 2. Chemical composition (%), viscosity of liquid phase and binary basicity index of the slags A, B, C, D e E.

Slags Al2O3 SiO2 CaO FeO MgO Liquid viscosity (P) Binary basicity % liquid
A 17- 21 9-14 50-65 3-8 >3 0,480 3-5 100
B 17-21 9-14 50-65 3-8 0 0,467 3-5 100
C 25-29 8-12 55-65 <1 0 0,973 5 - 10 94.8
D 25-29 8-12 50-65 <1 >3 0,993 5 - 10 96.3
E 25-29 8-12 55-65 1-4 0 0,871 5 - 10 92.5

Experimental procedure
The samples were sliced from a raw piece obtained from a plate. The raw piece was obtained from the first plate in the
starting of continuous casting steel machine. The weight of each specimen was about 1.0kg and it was enough for two
experiments. One portion was reserved to perform measurements of the initial level of inclusions. In Figure 5 is presented
some samples obtained and each part received a designation that allowed to identify the position that it was removed.

Figure 5. Macroscopic photograph of the parts obtained from the plate in the continuous casting steel machine.

After the initial preparation of the synthetic slags and steel samples, the experiments were carried out. Figure 6 schematically
shows the experimental apparatus. For the experiments the steel was placed in a carbon magnesium oxide crucible (MgO-C)
with internal diameter of 35 mm and 70 mm in height inserted into an alumina crucible. The MgO-C crucibles were made of
bricks designed for the slag line in blast oxygen furnace (BOF) converters. During the experiments, the temperature was
measured with a thermocouple positioned inside the metal and fixed at 1600oC.

Figure 6. Schematic design of the experimental apparatus for the study.

2122 © 2019 by the Association for Iron & Steel Technology.

In addition, a flow of argon was maintained to prevent oxidation of the steel. After reaching the temperature, synthetic slag
was added which was kept on the melted steel during 5 min. Stirring of the system was provided by the induction furnace. At
the end of the each experiment the MgO crucible with steel was removed from the furnace and its external wall was cooled in
water. The steel samples were cut lengthwise for analysis and measuring the level of the inclusions. For each slag were
performed at least 3 experiments.

After the experiments, the inclusion removal index (I) was calculated following equation 1:

(1)

Where ni is the initial number of inclusions per square millimeter initial and nf is the final number of inclusions per square
millimeter.

Characterization
All samples were characterized by optical microscopy (OM) where the concentration of inclusions per unit of area was
measured. Later these same samples were characterized by the Automated Steel Cleanliness Analysis Tool (ASCAT).

DISCUSSION

Figure 7 compares the mean level concentrations of inclusions in the steel using the optical microscope. The initial and final
levels were 150 inc/mm2 and 69 inc/mm² respectively with a standard deviation of 69 inc/mm2 and 43 inc/mm2. Thus, the
conclusion is that the experiments in overall promote the remove of the inclusions. However, it was not possible to establish
how each variable such as slag type, FeO concentration and MgO concentration play on the feasibility of the slags removing
inclusions.

Figure 7. Initial level of inclusions per unit of area for all experiments - OM.

The results obtained for ASCAT are shown in Figure 8 and the initial inclusion level was of 19 inc/mm2 with an average
standard deviation of 11 inc/mm2 was found. The concentration of inclusions after the experiments was 33 inc/mm2 with a
standard deviation of 16 inc/mm2. Thus, according to this second measurement technique, it is seeming that overall the
experiments were not efficient for remove the inclusions.

© 2019 by the Association for Iron & Steel Technology. 2123

 Figure 8. Initial and final concentration of inclusions per unit area for all experiments - ASCAT.

The results obtained by the ASCAT system are quite different from those found by the optical microscopy measurements
where the levels of inclusions were about 2 to 8 greater. This pattern shows that ASCAT system is not able for compute all
inclusions therefore, a reduced number of inclusions was identified. Perhaps this behavior is due to the ASCAT not identify all
inclusions with size less than 2 μm besides the counting system using an optical microscopy counts inclusions from 1.5 μm
diameter. In Figure 9 are summarized all size measurements performed before the experiments. It is possible to conclude that
the size distribution curves obtained by the two ways has expressive difference as can be seen in the shape of the curves and
the absolute amount for each size range. The size distribution for the samples after the experiments are very similar.

Figure 9. Inclusion size distribution before experiments. (a) OM (b) ASCAT.

2124 © 2019 by the Association for Iron & Steel Technology.

The MgO and CaO influence on slags with FeO
Figure 10 compares slags with MgO (A) and without MgO (B) and with the presence of FeO. There is a high variability of the
results of both materials that prevent to get conclusions clearly. Sometime a good behavior is observed and sometimes not that
is, the result is not predictable. These slags have, according to thermodynamic calculations, the lowest viscosities, they
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Figure 10. Influence of MgO on the removal inclusion index using slags with FeO. Slag with MgO - A and slag without MgO
– B - OM.

Still considering the aspect of how the FeO acts in the process, in the Figure 11a compares the removal rates for the slag C
and D with low FeO. We can realize that both mixtures have the capacity to remove inclusions, but in a modest index. The
searching for slags able to remove inclusions with FeO is very important from the industrial point of view, because it is very
difficult to obtain slags with low content or without FeO in a real process. In Figures 10b and 10c show a comparative result
with slag containing and no containing MgO independent of the presence of other compounds. It can be noticed that the best
performance slag is "E" where the highest levels of removal of inclusions were reached, which averaged of 81% efficiency,
which corresponds to 38 inc/mm2 for the final level of inclusions. The slag E has the highest CaO content and an intermediate
concentration of FeO according to the ranges presented in Table 2. Also, in the range of the initial inclusion density higher
than 100 inc/mm2, a best result was to slag (E) too, which does not present the lowest viscosity, different of the literature
prediction [1,2,7]. In fact, it was not possible to correlate the viscosity with the inclusion removal index. Therefore, there
must be other variables that are equally important for the absorption of the inclusions, possibly associated with the phases
present in the slag and the type of inclusion. An important aspect is that the slag (E) is the one with the highest concentration
of CaO among all and according to the literature [1] and thermodynamic simulations, the increase of CaO in the slag should
favor the removal of the inclusions.

Now considering the measurement performed using the ASCAT as an analysis tool, it seems that there is an effect of the
initial density of the inclusions in the removal process, that is, when the steel is cleaner it is harder to remove inclusions as
shown in Figure 12. The results also show that when the inclusion level is lower than 3 inc/mm2 it is very difficult arrest the
inclusions to the slag and under this condition in some experiments was observed an adverse result where the inclusion level
increases as shown in Figure 12b. When the initial concentration is higher than3 inc/mm2 we have found that only 6
measurements in 67 (~ 9%) gave an adverse inclusion removal index. At concentrations below 3 inc/mm2, the index was 360
inefficient measurements in 662 (~ 54%). The result here shows that eliminating inclusions of steels with an initial level in
the range of 3 to 8 inc/mm2 is relatively simple and any slag appears to be efficient. But now the challenge will be adding
further knowledge and understand the cleaning mechanisms below these limits. For measurements made using MO the
results are similar.

© 2019 by the Association for Iron & Steel Technology. 2125

 Figure 11. Influence of the FeO and MgO on the removal index of inclusions – OM. (a) Slags without FeO, (b) Slags
with MgO. (c) Slags without MgO.

Figure 12. General index of all inclusion removal as function of the initial level – ASCAT (a) all universe of initial level (b)
initial level of inclusion below of 3 inc / mm2.

2126 © 2019 by the Association for Iron & Steel Technology.

Type of inclusions
Figures 13a and 13b compare the measurements performed by the ASCAT method in the experiments using slag A and B
respectively. The results obtained before and after the experiments in both cases show an increase in the concentration of
inclusions with formation mainly of spinel, Mg and Misc rich phases. Also, for both slags it was found the ability to remove
Ti-based inclusions. The initial level of inclusions for the steels used with blend A was higher and this may explain their
higher efficiency. The slag B was able to remove Ti and Si inclusions with almost 100% of efficiency. Comparing the two
results and discounting the spinel, rich phases of Mg we have that the mixture that presented the best index of removal of
inclusions was the A with 14.8% of removal of the total of inclusions against 3.8% for the mixture B.

Figure 13. Level of main inclusions find out in the experiments – ASCAT (a) A e (b) B.

Figure 14 shows the performance of the mixtures as a function of the removal index given by equation 1 and the processes
enabled the removal of Solid Alumina, Al / Ti type inclusions with excellent efficiency. For some inclusions with low
concentration also it was systematically possibly eliminate as shown the results obtained for AlTi-MnS. The mixture having
MgO is A and this is the one that showed a better performance when discounting the phase formation containing spinels and
Mg rich. Therefore, it is believed that its inclusions removal capacity is better, however we have here again a suggestion that
the presence of MgO promotes the formation of new inclusions, damaging the process. This behavior was also observed in
the results obtained by MO as shown in the comparison of Figure 11c with Figure 11b.

Figure 14. Inclusion removal index - ASCAT (a) use of mixture A and (b) mixture B.

© 2019 by the Association for Iron & Steel Technology. 2127

In Figure 15 the results of the nature of the inclusions formed for the best synthetic slag - E are presented. Again, there is
clear perception of the formation of many spinels, however most inclusions were removed, especially those rich in Ti, Al,
and P. The ones with the lowest removal rate were Al/Ti type. It may be pre-mature to state, but what these results point out is
that there is a complex relationship between phases based on Mg. Thus, the control of compounds containing this element
seems to be one of the main aspects to be effectively studied in the future and that in turn will allow a better predictability of
the best slag feasible to arrest inclusions.

Figure 15. Type of inclusions for experiments with type E slag - ASCAT (a) Average concentration of the main inclusions
found in the experiments. (b) Inclusion removal index by type of inclusion.

CONCLUSIONS

Disregarding the presence of spinels and Mg rich phases, the E mixture was the most efficient to remove inclusions reaching
77% efficiency, including removal of inclusions under low concentrations. It was the slag that showed the best performance.
Corelate the viscosity of the slags with the inclusion removal performance was not possible.

The inclusions that are significantly removed are: Ti rich, Solid Alumina, Ti/Al, Al/Ti. But Al/Ti inclusion types looks the
hardest to be arrested.

Inclusions of differs type are generated during the experiments, disregarding the spinels and Mg rich phases, the inclusions
that most form are: Al/Ti, Misc, Solid Alumina. During the experiments it was observed a strong trend to form Mg and
spinel-rich phases.

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ACKNOWLEDGMENTS

We are gratefully to the Brazilian government agencies for research development: FAPES-Fundação de Amparo a Pesquisa-
ES-Brasil, CNPq-Conselho Nacional de Desenvolvimento Científico e Tecnológico, Capes-Coordenação de Aperfeiçoamento
de Pessoal de Nível Superior and FINEP-Financiadora de Estudos e Projetos for their collaboration and financial support.

2128 © 2019 by the Association for Iron & Steel Technology.

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