Inclusion Evolution and Removal in Ladle Refining

R. J. O’Malley
Iverson Chair Professor and
Director of the PSMRC
Materials Science & Engineering
Missouri University of Science & Technology
1400 N. Bishop Ave.
Rolla, MO 65409
omalleyr@mst.edu
(573) 341-7683

Abstract

The production of steels with low total oxygen content and preferred oxide morphologies
requires effective inclusion removal during ladle treatment after deoxidation and control of the
evolution of the inclusion population during ladle processing and steel transport. As demands
for increased steel cleanliness continue to grow, ongoing research on the behavior of inclusion
populations in the ladle during ladle treatment has continued to advance our understanding of the
ladle treatment process. This paper provides an introductory overview of inclusion behavior in
the ladle along with a review of the some of the ongoing research in the area of ladle treatment
and the factors that influence the evolution and removal of inclusions.
1. Steps in Ladle Treatment

The ladle treatment process is a key process for the production of steels with low inclusion
content and an inclusion composition and morphology that is not detrimental to the product or
its’ manufacturing process. However, the ladle treatment process also serves several other
functions that, at times, can be in conflict with clean steel production. The most common ladle
treatment steps include deoxidation of the steel and the slag, desulfurization of the steel, alloying
the steel, adjusting the steel temperature for shipment to the caster, control of dissolved gases
such as nitrogen and hydrogen, inclusion modification, and inclusion removal, as shown in
Figure 1.

Figure 1 – Steps in Ladle Treatment

The type of deoxidation practice employed in the steelmaking process plays an important role in
the type of the inclusions formed during ladle treatment. For many bar and structural products,
the steel is deoxidized with silicon and manganese (Mn-Si killed) while for sheet, plate and
special bar quality products, the steel is deoxidized with aluminum (Al killed). Some aluminum
killed steels are also treated with calcium to modify the alumina inclusions and sulfur containing
inclusions to improve castability and mechanical properties of the product. The inclusions that
evolve during ladle treatment can be fully solid, fully liquid or a mixture of solid and liquid.
They can also exist as a single phase or as a multiphase inclusion. Generally, liquid inclusions
are less likely to induce clogging than solid inclusions during continuous casting. However, the
tendency for inclusions to agglomerate and clog is highly dependent upon the interfacial energies
and contact angles between the specific inclusion-metal-gas-refractory system [1-3].

In some steelmaking processes, such as in integrated steelmaking operations, sulfur can be

removed by hot metal pretreatment while the oxygen activity is low [4, 5]. As such, there is less
need for sulfur removal during ladle treatment in the integrated steelmaking process. In electric
furnace steelmaking, however, sulfur removal must be performed during ladle treatment after the
steel and slag are fully deoxidized. This sulfur removal normally requires a more aggressive
deoxidation practice and strong stirring to achieve low sulfur levels in the steel. The processing
requirements for desulfurization in the ladle can influence the composition and morphology of
the inclusions formed in the process. For example, Al2MgO4 spinel inclusions will readily form
in aluminum killed steels that are subjected to a strong desulfurization treatment, while Al2O3
inclusions are more common in steels that are not subjected to a strong deoxidation and
desulfurization treatment [6, 7].

2. Inclusion Formation During Deoxidation

In order for steel to be cast continuously, dissolved oxygen in the steel must be reduced
sufficiently to avoid CO gas evolution during solidification. The most common elements used in
steel deoxidation are manganese, silicon, aluminum, calcium [8]. Complex deoxidation practices
may be employed that combine these deoxidant additions as shown in Figure 2. In some cases,
titanium, zirconium and rare earths may also be used for deoxidation [9-11].

Figure 2. Deoxidation equilibria for silicon, manganese, aluminum and calcium [4, 8].

Equilibrium between various deoxidant additions and oxygen in steel can also be calculated for a
wide range of elements and over a wide range of concentrations and temperatures using
thermodynamic software [12, 13]. This software is capable of calculating equilibrium conditions
for complex deoxidation and can also account for higher order solute atom interactions in steel
that lead to the retrograde oxygen solubility observed with strong deoxidants [13] shown in
Figure 3. It must be recognized, however, that the plots presented in Figures 2 and 3 are plots of
the dissolved deoxidant and oxygen concentrations in the steel that are in equilibrium with the
deoxidation product and that it excludes the oxygen and deoxidant contained in inclusions. As
shown in Figure 4, it can take some time to approach equilibrium concentrations in the bulk steel
composition as it takes some time for inclusions to agglomerate and float from the steel.

The oxygen content of the steel can vary widely prior to deoxidation. Typical BOF and EAF
oxygen levels at tap can range from 200 to 800 ppm oxygen. In addition, partial deoxidation is
sometimes performed during tapping in many operations using manganese, silicon and/or
aluminum. When deoxidant is added to the steel, the dissolved oxygen in the steel reacts with
the deoxidant addition to form an oxide:
 xM(in steel) + yO(in steel) = MxOy(inclusion) (1)

Figure 3. Deoxidation equilibria at high deoxidant concentrations [13].

Figure 4. Dissolved and total oxygen content during ladle processing [14].

Nucleation of oxides can occur by homogeneous nucleation, particularly when the level of
supersaturation of the dissolved metal and oxygen is high, or it can occur by heterogeneous
nucleation on inclusions formed earlier during the steelmaking process, on argon bubbles used to
stir the ladle or on the refractory walls of the ladle [15]. The rate of nucleation is influenced by
the level of supersaturation and the interfacial energy of the deoxidation product in contact with
steel. Zhang [16] provides a good overview of the mechanisms of nucleation and growth for a
pure oxide inclusion assuming homogeneous nucleation. The supersaturation ratio, P, and the
interfacial energy, s, between the steel and the oxide both influence the critical radius for
nucleation, as shown in equation 3, and thereby influence the size and number of inclusions
initially formed at the onset of deoxidation.
 # %
!" !$
P= # !% (2)
!" $ &'

,s-.
𝑟) = (3)
/0 12 P

Here, 𝑎4 is the activity of the deoxidant in molten steel at the moment when deoxidant is added,
𝑎5 is the activity of dissolved oxygen in molten steel at the moment when deoxidant is added, 𝐾7
is the equilibrium constant for equation (1), 𝑣9 is the molar volume of the oxide, 𝑅 is the ideal
gas constant and 𝑇 is absolute temperature. It is important to note that the interfacial energy
between the steel and the deoxidation product, s, is not necessarily a constant in equation (3),
but can also be a function of the oxygen content in the steel as shown in Figure 5 [17] or the
concentration of other surface active elements. This dependence, which differs for different
deoxidant systems, also influences the size and number of inclusions nucleated during
deoxidation.

Figure 5. Effect of oxygen content in liquid iron on the interfacial

energy between liquid iron and a-alumina [17].

It is generally accepted that nucleation occurs very quickly upon initial addition of deoxidant and
that both homogeneous and heterogeneous nucleation can occur [16, 18, 19]. Wakoh and
Sano[20] employed a special sampling device to investigate inclusions formed immediately after
aluminum deoxidation by quenching the steel immediately (~ 1 second) after the deoxidation
event. The investigators found a strong relationship between the level of oxygen and the size of
the inclusions formed and provided evidence that the early stages of inclusion formation was
controlled by oxygen diffusion in the liquid steel.

It is interesting to note that the time required to reach a uniform composition in an argon stirred
ladle is on the order of minutes [4, 21], while the time for nucleation is generally on the order of
0.1 second or less [22, 23], as shown in Figure 6. This implies that a wide range of levels of
supersaturation can exist during the deoxidation process in different locations within the ladle as
the deoxidant addition is mixed and dispersed in the ladle. This can lead to the formation of a
range of possible inclusion morphologies in the steel bath, as shown in Figures 7 and 8,
depending upon the local deoxidant concentration and oxygen supersaturation levels that exist in
different regions within the ladle [19, 23, 24].

Nucleation can continue to occur until supersaturation is no longer present. At this point, further
nucleation can only occur as the temperature of the steel decreases, when alloying elements are
added to the steel or when oxygen is re-introduced into the steel during reoxidation events.
Under these conditions, the level of supersaturation is generally much lower and heterogeneous
nucleation of new oxides onto pre-existing inclusions is generally more favorable.

Figure 6. Stages and times for inclusion nucleation and growth[22].

Figure 7. Effect of oxygen and deoxidant activities on inclusion morphology [23, 25].
 Figure 8. Alumina inclusion morphologies at various starting oxygen levels
in liquid iron just after aluminum deoxidation [19].

3. Inclusion Evolution after Deoxidation

Coarsening, Agglomeration and Removal of Inclusions

Once a population of inclusions is nucleated, the inclusions can grow by a variety of
mechanisms. The average particle size of the inclusion population can increase through
Ostwald-ripening, continued heterogeneous nucleation on previously nucleated inclusions and
through particle agglomeration. Particle collisions that lead to agglomeration can occur by
Brownian motion, turbulent motion, velocity gradients and Stokes collisions [15, 16, 26] More
recently, Sasai [27, 28] has proposed that cavity bridges can also promote attraction and
agglomeration of non-wetting particles, Figure 9, based on laboratory experiments that directly
measured the attraction forces between oxides in molten steel.

Figure 9. Cavity bridge mechanism of particle agglomeration, Sasai [27].

The size of the inclusions and their density drives the removal of inclusions from the steel by
flotation. Stokes’ law provides a rough estimate of the effects of inclusion diameter and particle
density on flotation rate:

<= >?& @>A B

u= , NRe < 1 (2)
7CD

where u is the flotation rate of the inclusion (m/s), d is the diameter of the inclusion (m), ρFe and
ρi are the density of molten steel and the inclusion, respectively (kg/m3), g is gravitational
acceleration (m/s2), and µ is the viscosity of molten steel (kg/(m·s)) and NRe is the Reynolds
number. The flotation rate is strongly favored by a large inclusion diameter and a low inclusion
density relative to the liquid steel density. Many investigators have developed more complex
models for inclusion flotation that account for non-laminar flow conditions and non-spherical
and clustered geometries [29, 30].

Rising bubbles from argon stirring also promote the removal of inclusions if wetting between the
inclusion and the argon bubble is favorable for attachment [31]. The fluid flows induced by
argon stirring or electromagnetic stirring can also promote inclusion transport and removal to the
slag layer or the ladle wall. An overview of these mechanisms for inclusion growth and removal
from the ladle is presented in Figure 10 [16].

Figure 10. Inclusion growth and removal mechanisms, Zhang, Pluschkell, and Thomas [16].

The effectiveness of argon stirring on inclusion removal depends on many factors, such as the
porous plug location, number of plugs, the size of the ladle, the intensity of the stirring, and the
contact angle of the inclusion with the steel and stirring gas [15, 32-35]. Table I shows some
typical contact angles [36] for oxides in liquid steel. Note that, in general, liquid oxide
inclusions tend to have much lower contact angles than solid oxide inclusions and generally have
less than a 90 degree wetting angle. This has implications for particle agglomeration and bubble
attachment mechanisms that influence the rate of inclusion removal from the ladle.

Table I. Contact angles of various oxides with liquid steel and argon [36].

Arai, et.al.[31], have demonstrated that the rate of removal of particles from a fluid by gas
bubbling is very dependent on the wetting angle of the particle-fluid-gas in a water model
system, and that the removal rate drops sharply when the wetting angle drops below 90 degrees,
as shown in Figure 11. Similar effects have been observed in steel systems as well. Argon
bubbling has also been shown to selectively remove under-modified solid calcium aluminate
inclusions from an inclusion population in the continuous caster tundish [6] and argon stirring
prior to calcium treatment has been shown to be more effective at removing inclusions than
argon stirring after calcium treatment [6], for example.

Figure 11. Effect of wetting angle on the rate of removal of

particles from water with argon bubbling [31].
Both inclusion agglomeration and bubble attachment mechanisms depend upon the interfacial
energy and wetting angle between inclusions and the liquid steel and mechanisms that promote
inclusion agglomeration and growth. Bubble attachment and cavity bridge agglomeration are
both favored by a large contact angle, suggesting that many solid inclusions are easier to remove
from the ladle than liquid inclusions [1]. The morphology of the solid inclusions can also
influence agglomeration and flotation, as demonstrated by Zheng in Figure 12 [2].

Figure 12. Effect of alumina morphology on clustering tendency [2].

Macroscopically, the inclusion removal from the ladle can be observed by monitoring the total
oxygen content of the steel using LECO® or PDA-OES analysis or by evaluating the number or
area density of the inclusions using SEM automated feature analysis [6, 37]. For a given stirring
intensity, stir configuration and inclusion population, longer rinse stir times normally result in
progressively more inclusion removal, as shown in Figure 13. This is true both for argon stirring
and stirring by other methods such as electromagnetic stirring (EMS), as shown in Figure 14.

Figure 13. Inclusion content vs time during soft stirring in the ladle with argon [6, 38]
 Figure 14. Effect of electromagnetic stirring power on inclusion removal [39].

Figure 14 also shows the importance of controlling the intensity of stirring in the ladle. While
increasing stirring intensity leads to increased rates of inclusion removal, excessively high stir
intensities can induce reoxidation by exposing the steel to air through the slag “eye” where the
slag is pushed back by the rising bubble plume or strong upward recirculating flow in EMS. This
condition can lead to a higher final inclusion content, as shown in Figure 14.

More recently, SEM-AFA analysis has made it possible to analyze a large number of inclusions
in a sample in a reasonable time. This has allowed steelmakers to observe the size distribution
and population number density of inclusion populations at various stages in the process. Van
Ende, et.al., [40, 41] has shown that the shape of the inclusion size distribution changes with
time, forming a log normal distribution early in the inclusion population’s life cycle and evolving
to a power law or fractal size distribution later in the population’s life cycle when active
nucleation is no longer taking place. The evolution of the inclusion population distribution with
time after deoxidation is shown in Figure 15 for increasing times, based on (a) observations from
plant data [40] and (b) from theoretical calculations of inclusion nucleation and growth [42].

(a) (b)
Figure 15. Changes in the size distribution of an inclusion population with time [40, 42].
Several investigators have reported similar trends in the evolution of the shape of the inclusion
population in ladle deoxidation using models for nucleation and growth of inclusions during
deoxidation in the ladle [19, 26, 32] and by direct experimental observation [43-45].
Observations of the shape of inclusion size distributions have been used successfully to identify
reoxidation events, where oxygen from the air generates a new population of reoxidation
inclusions that have a log normal distribution. On a log-log plot, this new population of
reoxidation inclusions will deviate from linearity, as shown in Figure 16(a) for conditions of a
tundish first fill [45] and eventually subsiding and re-establishing a linear distribution in Figure
16(b). Similar observations have been made in the ladle after additions are made [46].

Figure 16. Change in inclusion population density distribution

shape resulting from reoxidation in a caster tundish [45].

The type of deoxidant and the conditions of supersaturation employed in the deoxidation process
have a strong influence on the rate at which the inclusion population changes over time. Xuan,
et.al., [47] has observed a rapid increase in diameter and reduction of the number of inclusions
with time in Al deoxidized steels and little change in diameter and number with time in Ti and
complex Ti-Al steels, Figure 17, while Kang, et.al., [48] has reported large differences in the
agglomeration rate of different inclusion inclusions in steel using laser confocal microscopy.

Figure 17. Single inclusion/cluster size distribution after ladle deoxidation

with (a) Ti, (b) Al, and (c) Ti/Al [47].
Figure 17 illustrates the importance of agglomeration on inclusion removal. In Figure 17(b), the
size distribution of alumina clusters is observed to shift to progressively larger diameters and
lower inclusion counts with time. By comparison, the size distribution of the Ti/Al complex
deoxidant, which is liquid with a low wetting angle, does not increase in diameter with time and
the inclusion count drops much more slowly with time because of the smaller overall diameter of
the population.

Once the inclusions are transported to the slag layer in the ladle, the inclusions must contact and
become incorporated into the slag layer to be removed from the system. Lee, et.al., [49] studied
the rate of passage of inclusions through the slag-metal interface and the rate of dissolution of
inclusions in a CaO-Al2O3 slag using laser confocal microscopy. They observed that alumina
inclusions pass through the slag metal interface quickly, but that liquid MnO-SiO2-Al2O3
inclusions take much more time to pass through the interface and, in some cases, were not
captured by the slag at all. They also found the rate of inclusion dissolution in the slag was
diffusion controlled for alumina inclusions dissolving in the slag.

The rate of dissolution of Al2O3 and MgO inclusions in various slags has also been studied by
Park, et.al. [50], also using laser confocal microscopy. Park found that in some slag systems,
intermediate reaction products such as CaAl12O19 and Ca2Al2SiO7 formed on the inclusion
surface and slowed the dissolution rate of the inclusion into slag. The rate of dissolution of
Al2MgO4 oxide spinel in slags of various compositions has also been studied by Monaghan and
Chen [51]. They found that the rate of dissolution was controlled by diffusion in the slag and
was inversely related to the viscosity of the slag. If the time for passage through the slag–metal
interface or the dissolution rate in the slag is slow, the slag-metal interface can become a site for
solid inclusion agglomeration and re-emulsification of inclusions is possible [49].

Changes in Inclusion Composition During Ladle Treatment

So far, we have only discussed behavior of individual inclusion types in the ladle. In reality, the
composition and morphology of inclusions can change significantly during the course of ladle
treatment. Clearly, alloying additions made during ladle treatment can introduce elements that
influence the overall composition and number of inclusions that are present [6, 52]. Also,
additions such as calcium are employed specifically for the purpose of modifying inclusion
composition and morphology [53]. Even in the absence of these additions, the inclusions present
in a ladle after deoxidation can change composition over time through interactions with the slag
and refractories used in the ladle, or with the atmosphere if the ladle stirring is aggressive.

Mini-mills that produce aluminum killed steels with restricted sulfur levels often experience a
shift in inclusion chemistry during desulfurization. Under low oxygen conditions after
aluminum killing, argon stirring can promote the transfer of Mg from the slag and ladle
refractory lining to the steel. During this process, the alumina inclusions gradually pick up Mg
and the inclusion population gradually shifts from Al2O3 to Al2MgO4 spinel [6, 54, 55], as shown
in Figure 18. This exchange is influenced by the oxygen potential of the system and the
composition of the slag [56] as shown in Figure 19 [57]. Liu, et.al., [58] found that MgO in slag
and in the refractory both contribute to Mg pickup and spinel formation, but that slag had a
greater contribution to the pickup than the refractory.
 Figure 18. Evolution of spinel inclusions with argon stir time. Adapted from [46].

(a) (b)
Figure 19. (a) Effect of reducible oxide content in slag on inclusion MgO content and (b) rate of
MgO pickup in various heats reported by Mendez et.al. [57].

While calcium treatment is used commonly to convert solid alumina inclusions to liquid calcium
aluminate inclusions to improve castability, calcium treatment is also quite successful at
modifying solid spinel inclusions, as demonstrated by Verma, et.al., [59] and Pretorius [6].
These investigators have shown that spinel modification with Ca treatment reduces the Mg
content of the inclusion population and drives Mg back into solution in the liquid steel.
Subsequent exposure to reoxidation can result in the reformation of spinel inclusions through the
reoxidation of Mg in solution in the steel [6, 45] later in the process. These studies have also
shown that CaS formed during Ca treatment can serve to suppress the reformation spinels during
reoxidation by acting as a reservoir for calcium that can be released during reoxidation to further
modify newly formed alumina. Under these conditions, the presence of some CaS in the
inclusion population may be beneficial as long as it does not contribute to nozzle clogging during
casting.

It has also been shown that if the spinel inclusion population is high enough before Ca treatment,
solid MgO inclusions can also form along with liquid calcium aluminate inclusions after Ca
treatment, as shown in Figure 20 [46, 60]. This type of inclusion has been found to be very
detrimental in demanding products such as line-pipe steels [60]. Such conditions can arise when
aluminum killed steels are heavily aluminum deoxidized and held in contact with high MgO
slags and refractories for extended periods.

Figure 20. Evolution of inclusion composition (a) after deoxidation, (b) after desulfurization, (c)
after calcium treatment. Note presence of large MgO inclusions and CaS after Ca treatment [46].

Impurities in alloy additives also have a strong influence on the inclusion population and the
efficiency of inclusion removal. For example, the effects of Ca content of ferrosilicon on
inclusion composition and caster clogging sensitivity has been cited by several investigators [6,
52, 61, 62]. In some operations, Ca in ferrosilicon is managed to modify inclusions directly
without additional Ca treatment [6] while in other operations Ca in ferrosilicon must be restricted
to avoid changes in alumina morphology that promotes clogging [62]. The stage in the LMF
processing where inclusions are modified in relation to the application of soft argon stirring to
remove inclusions can have a pronounced effect on the inclusion removal efficiency. Argon
rinse stirring prior to Ca treatment, when solid inclusions are present, has been shown to be more
effective at removing inclusions than argon rinse stirring after Ca treatment, when the inclusions
have been modified to liquid calcium aluminates, for example [52].

4. Summary

The rate of inclusion agglomeration, flotation, capture and retention in the slag layer is a strong
function of the composition, morphology and phase (solid or liquid) of the inclusion population
in the ladle. While liquid inclusions readily dissolve in the slag once they pass through the slag-
metal interface, they are also less likely to agglomerate, float and pass to the slag layer than solid
inclusions while in the steel bath. This behavior, in general, leads to a lower coarsening and
flotation rate for liquid inclusions than solid inclusions and, hence, a lower overall inclusion
removal rate for liquid inclusions compared to solid inclusions.

The evolution of the inclusion population over time during ladle treatment can be complex.
Given that the effectiveness of inclusion removal by coagulation, bubble attachment and
interface capture is highly dependent upon the composition, phase, and morphology of the
inclusion population developed during the ladle treatment practice, it is evident that there are
time periods during ladle treatment where rinsing and flotation treatments will be more effective
than others. The ability to develop ladle treatment strategies to take advantage of these preferred
treatment times where inclusion coarsening and removal rates are the most rapid will ultimately
dependent upon the cleanliness of post-flotation-treatment additions, control of reoxidation and
slag entrainment during stirring and the effectiveness of reoxidation protection during steel
transfer.

5. Acknowledgements

The author would like to acknowledge the assistance of Sunday Abraham and Bill Jones for their
assistance in this work, and their efforts in organizing the memorial volume on clean steel in
honor of the late Kent D. Peaslee. I would also like to acknowledge the students, faculty and
industrial members of the Peaslee Steel Manufacturing Research Center (PSMRC) at Missouri
S&T for their tireless support. I would also like to thank Nucor Steel for their generous support
of the Iverson Chair for Steelmaking Technology at Missouri S&T.

6. References

1. Yin, H., et al., Characteristics of Agglomeration of Various Inclusion Particles on Molten

Steel Surface. ISIJ international, 1997. 37(10): p. 946-955.
2. Zheng, L., et al., Effect of Alumina Morphology on the Clustering of Alumina Inclusions
in Molten Iron. ISIJ International, 2016(0).
3. Abraham, S., R. Bodnar, and J. Raines, Inclusion Engineering and the Metallurgy of
Calcium Treatment. Iron &amp; Steel Technology, 2014: p. 57-68.
4. Fruehan, R., The Making, Shaping and Treating of Steel: Steelmaking and Refining
Volume. 11 ed, ed. R. Fruehan. Vol. 2. 2012. 144-145.
5. Fruehan, R.J., The Making, Shaping, and Treating of Steel: Ironmaking volume. 11 ed,
ed. R.J. Fruehan. Vol. 2. 2012: AISE Steel Foundation.
6. Pretorius, E., H. Oltmann, and B. Schart. An Overview of Steel Cleanliness From an
Industry Perspective. in AISTech 2013. 2013. AIST.
7. Harada, A., et al., Kinetic Analysis of Compositional Changes in Inclusions during Ladle
Refining. ISIJ International, 2014. 54(11): p. 2569-2577.
8. Turkdogan, E.T., Fundamentals of steelmaking. Vol. 614. 1996: Maney Pub.
9. Hideki Ono, K.N., Shingo Agawa, Toshio Ibuta, Ryota Maruo, and Tateo Usui,
Formation Conditions of Ti2O3, MgTi2O4, Mg2TiO4 and MgAl2O4 in Ti–Mg–Al
Complex Deoxidation of Molten Iron. steel research int., 2015. 86(No. 3): p. 241.
10. Lifeng Zhang, Y.R., Fundamentals of Steel Complex Deoxidation with Multiple
Deoxidizers, in 2015 AISTech Conference Proceedings, AIST, Editor. 2015, AIST.
11. Kwon, Y., J. Choi, and S. Sridhar, The morphology and chemistry evolution of inclusions
in Fe-Si-Al-O melts. Metallurgical and Materials Transactions B, 2011. 42(4): p. 814-
824.
12. Seetharaman, S., Treatise on process metallurgy, volume 3: industrial processes. Vol. 3.
2013: Newnes.
13. Jung, I.-H., S.A. Decterov, and A.D. Pelton, A thermodynamic model for deoxidation
equilibria in steel. Metallurgical and Materials Transactions B, 2004. 35(3): p. 493-507.
14. Torssell, K., Jernkontorets Ann., 1967. 151: p. 890-949.
15. Wang, L.T., et al., Mathematical model for growth and removal of inclusion in a multi-
tuyere ladle during gas-stirring. ISIJ international, 2005. 45(3): p. 331-337.
16. Zhang, L., W. Pluschkell, and B.G. Thomas. Nucleation and growth of alumina
inclusions during steel deoxidation. in Steelmaking Conference Proceedings. 2002.
Citeseer.
17. Wasai, K. and K. Mukai, Thermodynamics of nucleation and supersaturation for the
aluminum-deoxidation reaction in liquid iron. Metallurgical and Materials Transactions
B, 1999. 30(6): p. 1065-1074.
18. Sigworth, G.K. and J.F. Elliott, The conditions for nucleation of oxides during the silicon
deoxidation of steel. Metallurgical Transactions, 1973. 4(1): p. 105-113.
19. Jin, Y., Z. Liu, and R. Takata, Nucleation and Growth of Alumina Inclusion in Early
Stages of Deoxidation: Numerical Modeling. ISIJ international, 2010. 50(3): p. 371-379.
20. Wakoh, M. and N. Sano, Behavior of alumina inclusions just after deoxidation. ISIJ
international, 2007. 47(5): p. 627-632.
21. Mazumdar, D. and R. Guthrie, Mixing times and correlations for gas stirred ladle
systems. Iron &amp; steelmaker, 1999. 26(9): p. 89-96.
22. Lindborg, U., A collision model for the growth and separation of deoxidation products.
Trans. Metall. Soc. AIME, 1968. 242: p. 94.
23. ENDE, M.-A.V., Formation and Morphology of non-Metallic Inclusions in Aluminium
Killed Steels, in Department of Materials Science. 2010, Katholieke Universiteit Leuven:
Belgium. p. 261.
24. Dekkers, R., B. Blanpain, and P. Wollants, Crystal growth in liquid steel during
secondary metallurgy. Metallurgical and Materials Transactions B, 2003. 34(2): p. 161-
171.
25. Steinmetz, E. and H. Lindberg, Oxide Morphology at Manganese and Manganese-Silicon
Deoxidation. Archiv fur das Eisenhuttenwesen, 1976. 47(2): p. 71-76.
26. Kwon, Y.-J., J. Zhang, and H.-G. Lee, A CFD-based nucleation-growth-removal model
for inclusion behavior in a gas-agitated ladle during molten steel deoxidation. ISIJ
international, 2008. 48(7): p. 891-900.
27. Sasai, K., Interaction between Alumina Inclusions in Molten Steel Due to Cavity Bridge
Force. ISIJ International, 2016. 56(6): p. 1013-1022.
28. Sasai, K., Direct Measurement of Agglomeration Force Exerted between Alumina
Particles in Molten Steel. ISIJ International, 2014. 54(12): p. 2780-2789.
29. Tozawa, H., et al., Agglomeration and Flotation of Alumina Clusters in Molten Steel.
ISIJ international, 1999. 39(5): p. 426-434.
30. Doo, W.-C., et al. Analysis of alumina inclusions behavior in ladle refining. in 85 th
Steelmaking Conference. 2002.
31. Arai, H., et al., Model experiment on inclusion removal by bubble flotation accompanied
by particle coagulation in turbulent flow. ISIJ international, 2009. 49(7): p. 965-974.
32. Geng, D.-Q., H. Lei, and J.-C. He, Numerical Simulation for Collision and Growth of
Inclusions in Ladles Stirred with Different Porous Plug Configurations. ISIJ international,
2010. 50(11): p. 1597-1605.
33. Söder, M., Growth and removal of inclusions during ladle stirring. 2001.
34. Xu, X., G.A. Brooks, and W. Yang, Online analysis of stirring processes in ladle
metallurgy. Metallurgical and Materials Transactions B, 2010. 41(5): p. 1025-1032.
35. OHkubo, T.K.a.M., A Kinetic Study on Deoxidation of Steel. Trans. ISIJ, 1968. 8: p.
203-219.
36. Guthrie, R.I.L., Engineering in Process Metallurgy. 1992, Oxford: Clarendon Press.
37. M. Harris, O.A., S. Lekakh, R. O'Malley,et al. Improved Methodology for Automated
SEM/EDS Non-Metallic Inclusion Analysis of Mini-Mill and Foundry Steels. in
AISTech 2015. 2015. Cleveland, OH: AIST.
38. Martín, A., et al. Study about downgrading variables by inclusionary cleanliness in the
laddle furnace at ternium siderar. in Proceedings of the 7th International Conference on
Clean steel. 2007.
39. Zhang, L. and B.G. Thomas, State of the Art in Evaluation and Control of Steel
Cleanliness. ISIJ international, 2003. 43(3): p. 271-291.
40. Van Ende, M.-A., et al., Evolution of Non-Metallic Inclusions in Secondary Steelmaking:
Learning from Inclusion Size Distributions. ISIJ international, 2013. 53(11): p. 1974-
1982.
41. Van Ende, M.-A., et al., Morphology and growth of alumina inclusions in Fe–Al alloys at
low oxygen partial pressure. Ironmaking & Steelmaking, 2009. 36(3): p. 201–208.
42. Zhang, J. and H.-G. Lee, Numerical modeling of nucleation and growth of inclusions in
molten steel based on mean processing parameters. ISIJ international, 2004. 44(10): p.
1629-1638.
43. Zinngrebe, E., et al., Inclusion population evolution in Ti-alloyed Al-killed steel during
secondary steelmaking process. ISIJ international, 2012. 52(1): p. 52-61.
44. Van Ende, M.-A. and I.-H. Jung, A Kinetic Ladle Furnace Process Simulation Model:
Effective Equilibrium Reaction Zone Model Using FactSage Macro Processing.
Metallurgical and Materials Transactions B, 2016: p. 1-9.
45. Obinna Adaba, P.K., Ronald J. O’Malley, Simon N. Lekakh, Von L. Richards, Erik
Mantel, Randy Hall, and E. J.Ellis. Characteristics of Spinel Inclusions Formed after
Reoxidation of Calcium Treated Aluminum Killed Steel. in AISTech 2016. 2016.
Pittsburgh, PA.
46. Obinna Adaba, M.H., Ronald J. O’Malley, Simon N. Lekakh, Von L. Richards and Neil
Sutcliffe, An SEM/EDS Statistical Study of the Effect of Mini-Mill Practices on the
Inclusion Population in Liquid Steel, in 9th International Conference and Exhibition on
Clean Steel. 2015, Hungarian Mining and Metallurgical Society: Budapest, Hungary.
47. Xuan, C., A.V. Karasev, and P.G. Jönsson, Evaluation of Agglomeration Mechanisms of
Non-metallic Inclusions and Cluster Characteristics Produced by Ti/Al Complex
Deoxidation in Fe-10mass% Ni Alloy. ISIJ International, 2016. 56(0): p. 1204-1209.
48. Kang, Y., et al., Observation on physical growth of nonmetallic inclusion in liquid steel
during ladle treatment. Metallurgical and Materials Transactions B, 2011. 42(3): p. 522-
534.
49. Lee, S., et al., Separation and dissolution of Al2O3 inclusions at slag/metal interfaces.
Journal of non-crystalline solids, 2001. 282(1): p. 41-48.
50. Park, J.-H., I.-H. Jung, and H.-G. Lee, Dissolution behavior of Al2O3 and MgO
inclusions in the CaO-Al2O3-SiO2 slags: Formation of ring-like structure of MgAl2O4
and Ca2SiO4 around MgO inclusions. ISIJ international, 2006. 46(11): p. 1626-1634.
51. Monaghan, B.J. and L. Chen, Effect of changing slag composition on spinel inclusion
dissolution. Ironmaking & steelmaking, 2006. 33(4): p. 323-330.
52. A. Pitts, B.T., and L. Nastac, FeSi Residuals and Their Effects on Steel Cleanliness. Iron
and Steel Technology, 2015(October): p. 93-101.
53. Abraham, S., R. Bodnar, and J. Raines, Inclusion Engineering and the Metallurgy of
Calcium Treatment. Iron & Steel Technology, 2014: p. 57-68.
54. Björklund, J., A study of slag-steel-inclusion interaction during Ladle treatment. 2006.
55. Haoyuan Mu, B.A.W., Richard J. Fruehan, Reduction of Slags and Refractories by Al in
Steel and Inclusion Modification, in AISTech 2015, AIST, Editor. 2015, AIST. p. 3272-
3278.
56. Michelic, S., M. Hartl, and C. Bernhard. Thermodynamic and Experimental Study on the
Modification of Nonmetallic Inclusions Through the Contact with CaO-Al2O3-MgO
Slags. in Inclusion Symposium der AISTech. 2011.
57. Mendez, J., et al. Effect of process conditions on the evolution of MgO content of
inclusions during the production of calcium treated, aluminum killed steels. in 8th
International Conference on CLEAN STEEL. 2011.
58. Liu, C., F. Huang, and X. Wang, The Effect of Refining Slag and Refractory on Inclusion
Transformation in Extra Low Oxygen Steels. Metallurgical and Materials Transactions B,
2016. 47(2): p. 999-1009.
59. Verma, N., et al., Calcium Modification of Spinel Inclusions in Aluminum-Killed Steel:
Reaction Steps. Metallurgical and Materials Transactions B-Process Metallurgy and
Materials Processing Science, 2012. 43(4): p. 830-840.
60. Adaba, O., Formation and evolution of Spinel in aluminum killed calcium treated
linepipe steels, in Materials Science and Engineering. 2015, Missouri University of
Science and Technology.
61. Bi, Y., A. Karasev, and P.G. Jönsson, Investigations of inclusions in ferrochromium
alloys. Ironmaking & Steelmaking, 2014. 41(10): p. 756–762.
62. Asfahani, S.R.S.a.R.I., Control of Ca-Containing Inclusions in Al-Killed Steel Grades.
Iron & Steel Technology, 2013(October).