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Review Article
a r t i c l e i n f o a b s t r a c t
Article history: Non-metallic inclusions (NMIs) play a key role in many important properties of steel,
Received 11 January 2018 influencing both processing and application of steel products. In this work, the current
Accepted 19 April 2018 understanding of the origin and classification of NMIs is reviewed, highlighting the dra-
Available online 24 May 2018 matic development of the last decades. This includes the discussion of the thermodynamics
of inclusion formation and the current knowledge on the effects of melt shop processing
Keywords: variable on NMIs composition, amount and size distribution. The development of inclusion
Non-metallic inclusions engineering – tailoring the process to obtain the desired NMIs is highlighted and the devel-
Ladle metallurgy opment in selected areas – tire cord, springs and bearing steels as well as prevention of
Steelmaking nozzle clogging – is used to illustrate this development. The promising field of “oxide met-
Computational thermodynamics allurgy” is also discussed in the context of inclusion engineering. Finally, the difficulties in
Kinetics meaningfully characterizing and quantifying NMIs are briefly commented. In summary it
is concluded that inclusion control in steels has evolved significantly in the last decades.
This is due to the progress in understanding the interplay between thermodynamics, steel
and slag chemical composition as well as melt shop processing. This made possible the tai-
loring of non-metallic inclusions via processing, to optimize steel properties. Nonetheless,
some important problems remain and must still be solved to improve inclusion control and
optimization.
© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
E-mail: andre.costaesilva@gmail.com
https://doi.org/10.1016/j.jmrt.2018.04.003
2238-7854/© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
284 j m a t e r r e s t e c h n o l . 2 0 1 8;7(3):283–299
Wire
Inclusion
100µm
Acc.V Spot Magn Det WD
15.0 kV 6.0 318x BSE 8.2
Fig. 1 – Tire cord wire broken during wire drawing operation due to the presence of large hard inclusion. Inclusion is
indicated by arrow. SEM, scanning electron micrograph; BE, backscattered electrons [12].
refractories and casting pit material, for instance [7]. This, 2.2. Thermodynamic basis
however, has been significantly reduced in modern steels.
Nonetheless, it is still a problem that when students are As steelmaking temperatures are high, inclusion formation
introduced to the subject sometimes they end up believing reactions approach equilibrium. For this reason, thermody-
that the most important sources of non-metallic inclusions namics is an important tool in understanding their formation.
are “exogenous”. This does not mean that the interactions The thermodynamic fundamentals of NMI formation have
between the metal and refractories, for instance, are not been the subject of study for a long time [13,14] and are
relevant [8,9]. These interactions can indeed have a signifi- quite well known, e.g. refs. [6,15–18]. Nonetheless, it is worth
cant influence on the inclusions present in the steel. If the mentioning that there are still important discrepancies in the
definition of “exogenous” includes also, for instance, inclu- thermodynamic data related to the formation of, for instance,
sions originated from reoxidation from contact with air and alumina inclusions [19,20]. This may not be a problem for the
those resulting from entrained slag interacting with the liquid usual range of aluminum application as deoxidant, but it does
metal, as proposed in [10], the range of “exogenous” inclu- introduce important uncertainties in the processing of the
sions expands considerably. This is probably a more adequate new generation of high Al high Mn steels, for instance [21].
definition of “exogenous” inclusions. However, not only these The problem is also complicated in the case of elements with
inclusions are changed to a substantial extent during the limited solubility in iron such as Mg and Ca [18,22]. For these
process but, in some cases, it can be argued that they are elements, significant discussion still prevails with respect to
“part of the process”. Thus, it is debatable to which extent key thermodynamic data relevant for the study of reactions
the “exogenous”–“endogenous” classification helps or further in steelmaking. The application of computational thermody-
confuses the issue. namics has provided, in recent decades, important insight in
Finally, a common way of classification of NMIs is related the solution of complex problems. These used to be rather
to the inclusion size: thus, inclusions can be classified as difficult to handle with more conventional calculation tech-
macro and micro inclusions. One must be aware that, to niques. General aspects and examples of the application of
have a sensible cutoff between sizes, Kiessling’s proposal this technique to steels and steelmaking have been discussed,
should be used, when adopting this classification [2,11]: i.e., for instance, in refs. [23–27]. Examples of the application of the
an inclusion is a macro inclusion if it is large enough to technique to problems related to NMIs can be found in many
cause immediate failure of the product either during pro- publications such as refs. [28–32].
cessing or use, as for instance, the inclusion shown in Fig. 1.
All other inclusions should be classified as micro inclusions.
3. Formation, removal and control of NMIs
Thus, while important, this is a difficult classification to apply.
Frequently, sizes are defined arbitrarily to separate macro and
micro inclusions and the classification becomes difficult to The classification as primary and secondary is useful in the
justify. discussion of inclusion formation and removal. Removing
286 j m a t e r r e s t e c h n o l . 2 0 1 8;7(3):283–299
0.16 a
0.14
Oxygen in steel (%)
0.12 Oxygen a
%0i
in
0.1 solution
0.08 48
Total oxygen (Ot) 54
0.06
0.04 b
%0t
0.02 %0s c
0
%Als %Aladded
-2 0 2 4 6 8 10 12 14 16 b
Minutes after silicon addition 16
14
Fig. 4 – Oxide growth shapes as a function of the local activities of oxygen and aluminum (adapted from [40]).
Estimated average local oxygen activity (ppm)
High
600
400
200
100
O, ppm
100
80
60
800A
40
20 1250A
1000A
100 60
Ot <20 ppm
40
60
30
20
40
10
20
0
Mg Ai Ca Ti
100 VOD
for desulfurization. The increase of Ca and Mg content in the
inclusions is evidence of probable slag emulsification [71].
In the absence of a slag, excessive agitation with argon
was observed to cause re-entrainment of alumina inclusions
10-1
[70]. Thus, it seems clear that rinsing operations aimed at the
removal of NMIs from the liquid metal in the ladle, should be
performed at optimum selected agitation energies.
The importance of reoxidation for steel cleanness cannot
10-2
be overemphasized. Nadif and co-workers recently reviewed
the importance of reoxidation and the measures to control it
[72]. In recent decades, manufacturers have added many mea-
10-3 sures to control the most important sources of reoxidation
in and after ladle metallurgy: flat products producers regu-
100 101 102 103 104
larly use submerged entry nozzles (SEN) and ladle shroud to
Specific stirring power (W/t)
prevent contact of the steel stream with air. Tundish inerti-
Fig. 10 – Oxygen removal constant k in equation d%O dt
t
= −kt zation [73] and mold protection with inert gas, in special in
as a function of specific stirring power in different long products casting, are becoming standard for high qual-
secondary metallurgy reactors. Data mostly from [60,66,67] ity steels. Special attention is also given to shroud and valve
adapted from [64]. design to control air ingress caused by negative pressures in
valve systems [74].
The attachment of the inclusions to the sinks depends
on the industrial heats where measurements were made, it is mostly on surface tension and, on a secondary level, on the
difficult to speculate on the causes of this observation. ability of the sink to dissolve the inclusions. Most steelmaking
More recently, Zhang and Thomas [64] collected many slags, regardless of their composition, will wet oxide inclu-
results of the kinetic constant for the removal of oxide inclu- sions. This is due to the magnitude of the difference in the
sions as a function of agitation energy in a single graph surface energy between inclusion and steel and inclusion and
(Fig. 10). They included an envelope around the measure- slag. This issue has been discussed for a long time, at least
ments, to stress the existence of an optimum agitation. They since the work of [75] and others and has been summarized
also performed simulations that reproduced the expected by Olette in ref. [76]. The importance of the liquid fraction
behavior [65] represented by the envelope in Fig. 10. of the slag in promoting NMIs removal was clearly under-
The existence of an optimum agitation may be caused by stood very early [75] and was confirmed by clever experiments
reoxidation. Excessive stirring leads to the opening of an “eye” [77]. There remains, however, some controversy on the effect
in the slag causing steel exposure to the atmosphere [64] and of the slag viscosity. Nakajima and Okamura [78] proposed a
290 j m a t e r r e s t e c h n o l . 2 0 1 8;7(3):283–299
and avoid clogging during casting along with sulfide mod- 102
ification with calcium are also discussed in this section,
albeit they may be considered simpler cases of inclusion ppm O
Tire cords are usually made of silicon manganese steel wires. 100
icates. This requires rigid control of the alumina content %MgO in slag
of the slag, control of raw materials to prevent undesired 10
C2 0
C1 0
aluminum additions together with low slag binary basic-
ity, which contradicted the prevailing ladle furnace practice
C3 0
Fig. 15 – Complex calcium aluminate inclusion found in slabs treated with calcium to ensure good castability. Sulfide and
MgO were probably dissolved in the liquid inclusion during casting. Mg source is probably reduction from MgO in slag (see
discussion in item 4.2). Courtesy of C. Cicutti, Tenaris-Siderca.
5.0
A+CA6
4.5
CA2+CA6
4.0
CA2+L
3.5
ppm O
3.0 Liquid
inclusions
2.5
2.0 Ot=30ppm
Ot=15ppm Ot=20ppm
1.5
Fig. 16 – Complex calcium aluminate inclusion in fractured
sample from as-cast slab. Dendritic solidification is visible 1.0
0 5 10 15 20 25 30
in the outer layer of the inclusion. Courtesy of C. Cicutti,
Tenaris Siderca. ppm ca
efficiency of calcium treatment, as shown in Fig. 17. SLAG3 database. Points are experimental measurements of
oxygen in solution in heats without clogging events.
4.4. Oxide metallurgy
Adapted from [45].
tification (size, volume fraction and composition information) titatively NMI population to product properties and behavior.
several new methods and practices have been proposed and This is a vast field and will be discussed in a future publication.
have been reviewed in [64,187–192]. It is apparent that in many Thus, notwithstanding all the advances summarized in
cases more than one practice must be used to properly charac- this review, important problems and questions remain if the
terize and understand the effect of process on NMIs and then quality of steels is to continue improving in the next decades.
to correlate their effect with properties. This is understandable
since some properties seem to depend on the overall distribu-
Conflicts of interest
tion of inclusions and others, such as fatigue, depend on the
maximum sized inclusion. Furthermore even excluding low-
The author declares no conflicts of interest.
end products, the range of cleanness of steel products varies
significantly. Low-carbon aluminum killed (LCAK) steel have
around 40 ppm total oxygen content while bearing steels with Acknowledgements
around 5 ppm total oxygen are now typical. This results in a
dramatic difference in volume fraction of oxide inclusions, not The author thanks all his former and present students for
to mention sulfides. Extreme value statistics and its applica- inspiration and important contributions to the work on non-
tion are of paramount importance in fatigue. These methods metallic inclusions in steels. The collaboration of colleagues
are seldom included in usual reviews. For a review including in many steelmakers and research organizations is gratefully
these methods, the reader is referred to ref. [188]. The method acknowledged.
of inclusion rating using statistics of extremes adopted in the The support of CNPq, CAPES and FAPERJ during different
procedure proposed by Murakami [193] is widely used in the stages on the author’s work is also acknowledged.
area of fatigue, with very good results. It must be mentioned
that, in this method, there would be no limit to maximum references
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